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United States 
Environmental Protection 
Agency 


Office of Air Quality 
Planning And Standards 
Research Triangle Park, NC 27711 


EPA-454/R-98-013 
June 1998 


O EPA 


LOCATING AND ESTIMATING 
AIR EMISSIONS FROM SOURCES OF 
ARSENIC AND ARSENIC COMPOUNDS 


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TABLE OF CONTENTS 


Section Page 

LIST OF TABLES. viii 

LIST OF FIGURES.xi 

EXECUTIVE SUMMARY. xiv 

1.0 PURPOSE OF DOCUMENT .1-1 

2.0 OVERVIEW OF DOCUMENT CONTENTS.2-1 

3.0 BACKGROUND.. 3-1 

3.1 Physical And Chemical Nature Of Arsenic And Arsenic Compounds .3-1 

3.1.1 Inorganic Compounds .3-3 

3.1.2 Organic Arsenic Compounds.3-10 

3.2 Fate Of Arsenic ..;. . 3-14 

3.2.1 Fate of Arsenic in Soil.3-14 

3.2.2 Fate of Arsenic in Water .3-15 

3.2.3 Fate of Arsenic in Air.3-16 

3.2.4 Fate of Arsenic in Plants and Food .3-16 

3.3 Overview Of Production And Use.3-17 

3.3.1 Metallic Arsenic.3-19 

3.3.2 Arsenic Trioxide .3-19 

4.0 EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM 

COMBUSTION SOURCES .....4-1 

4.1 Stationary External Combustion .4-1 

4.1.1 Process Descriptions for Utility, Industrial, and Commercial Fuel 

Combustion .4-3 

4.1.2 Emission Factors for Utility, Industrial, and Commercial Fuel 

Combustion .4-15 

4.1.3 Source Locations . 4-33 

4.2 Hazardous Waste Incineration.4-35 

4.2.1 Process Description .4-36 

4.2.2 Emission Factors .4-43 

4.2.3 Source Location.4-43 


in 





























TABLE OF CONTENTS, continued 



SectiQn 

4.3 Municipal Waste Combustion.4-45 

4.3.1 Process Description. 4-45 

4.3.2 Emission Factors .4-52 

4.3.3 Source Location.4-56 

4.4 Sewage Sludge Incinerators. 4-56 

4.4.1 Process Description.4-56 

4.4.2 Emission Factors .4-63 

4.4.3 Source Location.4-66 

4.5 Medical Waste Incineration..4-66 

4.5.1 Process Description .4-66 

4.5.2 Emission Factors .4-74 

4.5.3 Source Location.4-74 

4.6 Crematories . 4-77 

4.6.1 Process Description ..4-77 

4.6.2 Emission Factors .4-77 

4.6.3 Source Locations .4-78 


4.7 Stationary Internal Combustion Sources.4-78 

4.7.1 Emissions.4-78 

4.7.2 Source Description.4-82 


5.0 EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM THE 

METALLURGICAL INDUSTRY....5-1 


5.1 Primary Lead Smelting ... 5-1 

5.1.1 Process Description. 5-1 

5.1.2 Emission Control Techniques . 5-4 

5.1.3 Emissions. 5.5 


5.2 Secondary Lead Smelting . 5.5 

5.2.1 Process Description . 5.5 

5.2.2 Emission Control Techniques . 5_17 

5.2.3 Emissions.. 

5.2.4 Source Locations . *01 


5.3 Primary Copper Production 

5.3.1 Source Description 

5.3.2 Process Description 

5.3.3 Emissions. 


5-21 

5-21 

5-23 

5-25 





































TABLE OF CONTENTS, continued 


Section Page 

5.3.4 Emission Control Techniques .5-28 

5.3.5 Source Location. v.*. .5-30 

5.4 Secondary Aluminum Operations .5-31 

5.4.1 Source Description.5-31 

5.4.2 Process Description. 5-31 

5.4.3 Emissions and Control. 5-36 

5.5 Ferroalloy Production .5-38 

5.5.1 Source Description.5-38 

5.5.2 Process Description.5-39 

5.5.3 Emissions and Controls.5-45 

5.6 Iron and Steel Foundries .5-47 

5.6.1 Process Description.5-47 

5.6.2 Emission Control Techniques . 5-52 

5.6.3 Emission Factors . 5-52 

5.6.4 Source Locations .5-52 

6.0 EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM THE PULP 

AND PAPER INDUSTRY .6-1 


6.1 Kraft Recovery Furnaces And Smelt-Dissolving Tanks .6-1 

6.1.1 Process Description.6-1 

6.1.2 Emission Factors .6-7 

6.1.3 Source Locations .6-7 

6.2 Lime Kilns. 6-7 

6.2.1 Process Description .6-7 

6.2.2 Emission Factors .6-11 

6.2.3 Source Locations .6-11 

6.3 Sulfite Recovery Furnaces.6-11 

6.3.1 Process Description .6-11 

6.3.2 Emission Factors .6-14 

6.3.3 Source Locations .6-14 

7.0 EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM 

OTHER SOURCES. ..7-1 

7.1 Glass Manufacturing .7-1 

7.1.1 Process Description .7-2 


v 


































TABLE OF CONTENTS, continued 


Section Eage 

# 

7.1.2 Emission Control Techniques .7-3 

7.1.3 Emissions. 7-3 

7.2 Municipal Solid Waste Landfills.7-4 

7.2.1 Process Description. 7-4 

7.2.2 Emission Control Techniques . 7-5 

7.2.3 Emission Factors . 7-6 

7.2.4 Source Locations.7-6 

7.3 Asphalt Concrete.7-6 

7.3.1 Process Description..7-6 

7.3.2 Emission Control Techniques .7-14 

7.3.3 Emission Factors .7-14 

7.3.4 Source Locations.7-14 

7.4 Abrasive Grain Processing.7-16 

7.4.1 Process Description.7-16 

7.4.2 Emission Control Techniques .7-19 

7.4.3 Emission Factors .7-19 

7.4.4 Source Locations .7-20 

7.5 Portland Cement Production . 1-20 

7.5.1 Process Description. 7-21 

7.5.2 Emission Control Techniques .7-24 

7.5.3 Emission Factors .7-25 

7.5.4 Source Locations. 1-26 

7.6 Open Burning Of Scrap Tires . 7.33 

7.6.1 Process Description. 7.33 

7.6.2 Emission Factors . 7.33 

7.6.3 Source Location. 7.33 

7.7 Grain Milling. l-2>4 

7.8 Process Heaters . 7_35 

7.9 Cotton Production and Ginning. 7 _ 3 g 

8.0 SOURCE TEST PROCEDURES . g _j 

8.1 Ambient Air Sampling Methods . 09 


vi 


































TABLE OF CONTENTS, continued 


Section Page 

8.1.1 Methodology for the Determination of Suspended Particulate 
Matter in the Atmosphere (High-Volume Method) and Modified 
Methodology for the Determination of Lead in Suspended 

Particulate Matter Collected from Ambient Air .8-2 

8.1.2 NIOSH Method 7300 - Methodology for the Determination of 

Elements by Inductively Coupled Plasma (ICP) ..8-4 

8.1.3 NIOSH Method 7900 - Methodology for the Determination of 
Arsenic and Compounds, as Arsenic, using Direct-Aspiration 

(Flame) Atomic Absorption Spectroscopy (AAS).8-5 

8.1.4 NIOSH Method 7901 - Methodology for the Determination of 

Arsenic Trioxide, as Arsenic, by Graphite Furnace Atomic 
Absorption (GFAA).8-5 

8.1.5 NIOSH Method 5022 - Methodology for the Determination of 

Organo-Arsenic Compounds by Ion Chromatography (IC)/Graphite 
Furnace Atomic Absorption (GFAA) .8-6 

8.2 Stationary Source Sampling Methods .8-6 

8.2.1 EPA Method 29 - Determination of Metals Emissions from 

Stationary Sources.8-7 

8.2.2 EPA Method 108 - Methodology for the Determination of 

Particulate and Gaseous Arsenic Emissions .8-9 

8.2.3 EPA BEF Method Section 3.0 - Methodology for the Determination 

of Metals Emissions in Exhaust Gases from Hazardous Waste 
Incineration and Similar Combustion Processes.8-9 

8.2.4 CARB Method 423 - Methodology for the Determination of 
Particulate and Gaseous Inorganic Arsenic Emissions from 

Stationary Sources.8-11 

8.2.5 CARB Draft Method 436 - Determination of Multiple Metals 

Emissions from Stationary Sources.8-11 

8.3 Analytical Techniques For The Measurement Of Arsenic.8-11 

8.3.1 Direct Aspiration (Flame) Atomic Absorption Spectroscopy (AAS) .8-12 

8.3.2 Graphite Furnace Atomic Absorption (GFAA) Spectroscopy.8-12 

8.3.3 Inductively Coupled Plasma (ICP) Atomic Emission Spectroscopy .. 8-13 

8.3.4 Hydride Generation Atomic Absorption (HGAA) Spectroscopy .... 8-13 

8.3.5 Ion Chromatography (IC)/GFAA.8-14 

APPENDICES 

Appendix A - Emission Factor Summary Table. A-l 


Vll 





















































LIST OF TABLES 


Table Page 

3-1 Physical Properties of Arsenic.3-2 

3-2 Important Arsenic-Bearing Minerals.3-3 

3-3 Common Arsenic Compounds.3-4 

3-4 Physical Properties of Arsenic Halides .3-6 

3-5 Physical Properties of Common Arsenic Sulfides.3-9 

3-6 Organic Arsenic Compounds.3-11 

3- 7 U.S. Imports for Consumption of Arsenicals, by Country.3-18 

4- 1 Arsenic Emission Factors for Wood Waste-Fired Utility Boilers.4-18 

4-2 Arsenic Emission Factors for Wood Waste-Fired Industrial Boilers .... . : . . 4-19 

4-3 Arsenic Emission Factors for Wood Waste-Fired Commercial/Institutional Boilers . 4-21 

4-4 Arsenic Emission Factors for Coal-Fired Utility Boilers.4-23 

4-5 Arsenic Emission Factors for Coal-Fired Industrial Boilers .4-25 

4-6 Arsenic Emission Factors for Coal-Fired Commercial/Institutional Boilers.4-27 

4-7 Arsenic Emission Factors for Oil-Fired Utility Boilers.4-28 

4-8 Arsenic Emission Factors for Oil-Fired Industrial Boilers . 4-29 

4-9 Arsenic Emission Factors for Oil-Fired Commercial/Institutional Boilers.4-30 

4-10 Arsenic Emission Factors for Waste Oil-Fired Industrial Boilers.4-31 

4-11 Arsenic Emission Factors for Waste Oil-Fired Commercial/Institutional Boilers .. . 4-32 

4-12 Arsenic Emission Factors for Solid Waste-Fired Utility Boilers. 4-34 

4-13 Arsenic Emission Factors for Hazardous Waste Incineration.4-44 

4-14 Arsenic Emission Factors for Municipal Waste Combustion Sources .4-53 


vm 






















LIST OF TABLES, continued 

Table Page 

4-15 Summary of Geographical Distribution of MWC Facilities (1997) . 4-57 

4-16 Arsenic Emission Factors for Sewage Sludge Incinerator Sources.4-64 

4-17 Arsenic Emission Factors for Medical Waste Incineration Sources .4-75 

4-18 Arsenic Emission Factor for Crematories .4-79 

4-19 1991 U.S. Crematory Locations by State.4-80 

4- 20 Arsenic Emission Factors for Internal Combustion Engines.4-81 

5- 1 Domestic Primary Lead Smelters And Refineries.5-2 

5-2 Arsenic Emission Factor for Primary Lead Smelting Facilities.5-6 

5-3 Arsenic Emission Factors for Secondary Lead Smelting Facilities.5-20 

5-4 U.S. Secondary Lead Smelters Grouped According to Annual Lead Production 

Capacity. 5-22 

5-5 Arsenic Emission Factors for Primary Copper Smelting Facilities.5-27 

5-6 Primary Copper Smelters in the United States.5-30 

5-7 Arsenic Emission Factors for Secondary Aluminum Production . 5-37 

5-8 Ferroalloy Processes and Respective Product Groups. 5-40 

5-9 Arsenic Emission Factors for Electric Arc Furnaces.5-46 

5- 10 Arsenic Emission Factors for Iron and Steel Foundries.5-53 

6- 1 Arsenic Emission Factors for Kraft Process Recovery Furnaces and Smelt 

Dissolving Tanks.6-8 

6-2 Distribution of Kraft Pulp Mills in the United States (1997). 6-9 

6-3 Arsenic Emission Factors for Lime Kilns .6-12 

6-4 Arsenic Emission Factors for Sulfite Process Recovery Furnaces . 6-15 


• IX 























LIST OF TABLES, continued 


Table Page 

6- 5 Distribution of Sulfite Pulp Mills in the United States (1997) . 6-15 

7- 1 Other Sources of Arsenic Emissions.7-2 

7-2 Arsenic Emission Factor for Glass Manufacturing.7-4 

7-3 Arsenic Emission Factor for Landfill Process Gas .7-7 

7-4 Arsenic Emission Factors from Asphalt Concrete Production .7-15 

7-5 Arsenic Emission Factor for Abrasive Grain Processing.7-20 

7-6 1995 U.S. Primary Abrasive Grain Manufacturer Locations by State.7-21 

7-7 Arsenic Emission Factors for Dry Process Portland Cement Kilns by Fuel and 

Waste Type ..7-26 

7-8 Arsenic Emission Factors for Portland Cement Manufacturing Facilities.7-27 

7-9 Portland Cement Production Facilities (1995). 7-28 

7-10 Arsenic Emission Factors for Open Burning of Scrap Tires.7-34 

7-11 Arsenic Emission Factors for Grain Milling .7-36 

7-12 Arsenic Emission Factors for Process Heaters .7-37 

A- 1 Summary of Emission Factors by Source Classification Codes . A-1 


. x 













































• . 






. 



















■ - • 

■ 

•2 ' 


' 











































- 

■ 



















































. 


















LIST OF FIGURES 


Fi gure Page 

4-1 Simplified Boiler Schematic .4-4 

4-2 Single Wall-Fired Boiler.4-6 

4-3 Simplified Atmospheric Fluidized Bed Combustor Process Flow Diagram.4-8 

4-4 Spreader Type Stoker-Fired Boiler .4-9 

4-5 Typical Process Component Options in a Hazardous Waste Incineration Facility ... 4-37 

4-6 Typical Liquid Injection Combustion Chamber .4-38 

4-7 Typical Rotary Kiln/Afterburner Combustion Chamber.4-40 

4-8 Typical Fixed-Hearth Combustion Chamber.4-41 

.4-9 Typical Mass Bum Waterwall Combustor.4-46 

4-10 Simplified Process Flow Diagram, Gas Cycle for a Mass Bum/Rotary Waterwall 

Combustor.4-47 

4-11 Mass Bum Refractory-Wall Combustor with Grate/Rotary Kiln .4-48 

4-12 Typical RDF-Fired Spreader Stoker Boiler.4-50 

4-13 Typical Modular Starved-Air Combustor with Transfer Rams.4-51 

4-14 Typical Multiple-Hearth Furnace....4-59 

4-15 Fluidized-Bed Combustor .4-61 

4-16 Controlled-Air Incinerator.4-68 

4-17 Excess-Air Incinerator.4-70 

4- 18 Rotary Kiln Incinerator .4-72 

5- 1 Typical Primary Lead-Processing Scheme.5-3 

5-2 Simplified Process Flow Diagram for Secondary Lead Smelting.5-8 

5-3 Cross-Sectional View of a Typical Stationary Reverberatory Furnace.5-10 


xi 























LIST OF FIGURES, continued 


Figure F a S? 

5-4 Cross-Section of a Typical Blast Furnace .i:.5-13 

5-5 Side View of a Typical Rotary Reverberatory Furnace.5-15 

5-6 Cross-Sectional View of an Electric Furnace for Processing Slag . 5-18 

5-7 Typical Primary Copper Smelter Flow Sheet ...5-24 

5-8 Copper Converter.5-26 

5-9 Fugitive Emission Sources at Primary Copper Smelters.5-29 

5-10 Typical Process Diagram for Pretreatment in the Secondary Aluminum Processing 

Industry .5-32 

5-11 Typical Process Flow Diagram for the Secondary Aluminum Processing Industry. . . 5-33 

5-12 Typical Ferroalloy Production Process .5-41 

5-13 Typical Submerged Arc Furnace Design.5-43 

5-14 Process Flow Diagram for a Typical Sand-Cast Iron and Steel Foundry.5-49 

5- 15 Emission Points in a Typical Iron and Steel Foundry .5-50 

6 - 1 Typical Kraft Pulping and Recovery Process .6-2 

6-2 Direct Contact Evaporator Recovery Boiler . 6-4 

6-3 Nondirect Contact Evaporator Recovery Boiler .6-5 

6-4 Process Flow Diagram for Lime Kiln .6-10 

6- 5 Process Diagram for Magnesium-Based Sulfite Pulping and Chemical Recovery ... 6-13 

7- 1 General Process Flow Diagram for Batch-Mix Asphalt Paving Plants.7-9 

7-2 General Process Flow Diagram for Drum-Mix Asphalt Paving Plants.7-12 

7-3 General Process Flow Diagram for Counterflow Drum-Mix Asphalt Paving Plants .7-13 


Xll 





















LIST OF FIGURES, continued 

Figure Page 

7-4 Flow Diagram for Abrasive Grain Processes. 7-18 

7- 5 Process Flow Diagram Of Portland Cement Manufacturing Process.7-22 

8- 1 Components of a High-Volume Ambient Air Sampler for Arsenic .8-3 

8-2 EPA Method 29, BIF Method, and CARB Draft Method 436 Sampling Train.8-8 

8-3 EPA Method 108 and CARB Method 423 Sampling Train .8-10 


Xlll 





























EXECUTIVE SUMMARY 


The 1990 Clean Air Act Amendments contain a list of 188 hazardous air 
pollutants (HAPs) which the U.S. Environmental Protection Agency must study, identify sources 
of, and determine if regulations are warranted. Of these HAPs, arsenic and arsenic compounds 
are the subject of this document. This document describes the properties of arsenic and arsenic 
compounds as air pollutants, defines production and use patterns, identifies source categories of 
air emissions, and provides emission factors. The document is a part of an ongoing EPA series 
designed to assist the general public at large, but primarily State/local air agencies, in 
identifying sources of HAPs and developing emissions estimates. 

Arsenic is emitted as an air pollutant from external combustion boilers, municipal and 
hazardous waste incineration, primary copper and zinc smelting, glass manufacturing, copper 
ore mining, and primary and secondary lead smelting. Emissions of arsenic from these 
activities are due to the presence of trace amounts of arsenic in fuels and materials being 
processed. In such cases, the emissions may be quite variable because the trace presence of 
arsenic is not constant. For instance, the concentration of arsenic in coal can vary by four 
orders of magnitude. Arsenic emissions also occur from agricultural chemical production and 
application, and also from metal processing due to the use of arsenic in these activities. 

In addition to the arsenic source information, information is provided that specifies how 
individual sources of arsenic may be tested to quantify air emissions. 


. xiv 

















. 

• > 

. • ... 

















■ 

; 
































' 















































SECTION 1.0 

PURPOSE OF DOCUMENT 


The Environmental Protection Agency (EPA) and State and local air pollution control 
agencies are becoming increasingly aware of the presence of substances in the ambient air that 
may be toxic at certain concentrations. This awareness has led to attempts to identify 
source/receptor relationships for these substances and to develop control programs to regulate 
toxic emissions. 

To assist groups interested in inventorying air emissions of various potentially toxic 
substances, EPA is preparing a series of documents that compiles available information on 
sources and emissions. Existing documents in the series are listed below. 


Substance 

Acrylonitrile 

Benzene 

Butadiene 

Cadmium 

Carbon Tetrachloride 
Chlorobenzene (update) 
Chloroform 

Chromium (supplement) 
Chromium 

Coal and Oil Combustion Sources 

Cyanide Compounds 

Dioxins and Furans 

Epichlorohydrin 

Ethylene Dichloride 

Ethylene Oxide 


EPA Publication Number 

EPA-450/4-84-007a 

EPA-450/R-98-011 

EPA-454/R-96-008 

EPA-454/R-93-040 

EPA-450/4-84-007b 

EPA-454/R-93-044 

EPA-450/4-84-007C 

EPA-450/2-89-002 

EPA-450/4-84-007g 

EPA-450/2-89-001 

EPA-454/R-93-041 

EPA-454/R-97-003 

EPA-450/4-84-007j 

EPA-450/4-84-007d 

EPA-450/4-84-0071 


1-1 




Substance 

EPA Publication Number 

Formaldehyde 

EPA-450/4-91-012 

Lead 

EPA-454/R-98-006 

Manganese 

EPA-450/4-84-007h 

Medical Waste Incinerators 

EPA-454/R-93-053 

Mercury and Mercury Compounds 

EPA-453/R-93-023 

Methyl Chloroform 

EPA-454/R-93-045 

Methyl Ethyl Ketone 

EPA-454/R-93-046 

Methylene Chloride 

EPA-454/R-93-006 

Municipal Waste Combustors 

EPA-450/2-89-006 

Nickel 

EPA-450/4-84-007f 

Perchloroethylene and 

T richloroethy lene 

EPA-450/2-89-013 

Phosgene 

EP A-450/4-84-007i 

Polychlorinated Biphenyls (PCBs) 

EPA-450/4-84-007n 

Polycyclic Organic Matter (POM) 

EPA-450/4-84-007p 

Sewage Sludge Incinerators 

EPA-450/2-90-009 

Styrene 

EPA-454/R-93-011 

Toluene 

EPA-454/R-93-047 

Vinylidene Chloride 

EPA-450/4-84-007k 

Xylenes 

EPA-454/R-93-048 


This document deals specifically with arsenic and arsenic compounds. Its intended 
audience includes Federal, State and local air pollution personnel and others who are interested in 
locating potential sources of arsenic and arsenic compounds and in making gross emission 
estimates of these air pollutants. 


With the 1990 Amendments to the Clean Air Act (CAA), arsenic and arsenic compounds 
were both recognized for their toxic characteristics and added to the list of hazardous air 
pollutants (HAPs) presented in Section 112(d) to be evaluated in the development of maximum 
achievable control technology (MACT) standards. In addition, many States also recognize 
arsenic and arsenic compounds as toxic pollutants, and some States may impose their own 
regulations, which can be more stringent than the federal ones. 


1-2 




Arsenic air emissions have also been affected by regulatory activity from other 
agencies-including the Occupational Safety and Health Administration (OSHA), where 
regulations for reducing arsenic exposure to a variety of worker categories are in effect. 

A concerted effort was made during the development of this document to coordinate with 
the current work that is underway at the Office of Air Quality Planning and Standards (OAQPS) 
in developing MACT standards. Data were also available from National Emission Standard for 
Hazardous Air Pollutants (NESHAP) project files for the regulations pertaining to arsenic 
emissions from glass manufacturing plants, primary copper smelters, and arsenic trioxide and 
metallic arsenic production facilities. 

Also, as a result of the California “Hot Spots” program and other State source testing 
efforts (where such information is available through EPA's Source Test Information Retrieval 
System [STIRS] database and its Factor Information Retrieval [FIRE] System), data have been 
documented from source tests performed to demonstrate, among other reasons, permit 
applicability Such programs have been valuable for acquiring source-specific emissions data. 

However, despite the data generated by these programs, the available data on some 
potential sources of arsenic emissions are limited and the configurations of many sources will not 
be the same as those described in this document. Therefore, this document is best used as a 
primer to inform air pollution personnel about: (1) the types of sources that may emit arsenic, 

(2) process variations that may be expected within these sources, and (3) available emissions 
information that indicates the potential for arsenic to be released into the air from each operation. 

The reader is strongly cautioned against using the emission factors or emissions 
information contained in this document to try to develop an exact assessment of emissions from 
any particular facility. Available data are insufficient to develop statistical estimates of the 
accuracy of these emission factors, so no estimate can be made of the error that could result when 
these factors are used to calculate emissions from any given facility. It is possible, in some cases, 
that order-of-magnitude differences could result between actual and calculated emissions, 
depending on differences in source configurations, control equipment, and operating practices. 


1-3 


Thus, in situations where an accurate assessment of arsenic emissions is necessary, source- 
specific information should be obtained to confirm the existence of particular emitting 
operations, the types and effectiveness of control measures, and the impact of operating practices. 
A source test should be considered as the best means to determine air emissions directly from a 
facility or operation. 

As standard procedure, L&E documents are sent to government, industry, and 
environmental groups wherever EPA is aware of expertise. These groups are given the 
opportunity to review a document, comment, and provide additional data where applicable. 
Although this document has undergone extensive review, there may still be shortcomings. 
Comments subsequent to publication are welcome and will be addressed based on available time 
and resources. In addition, any comments on the contents or usefulness of this document are 
welcome, as is any information on process descriptions, operating practices, control measures, 
and emissions information that would enable EPA to update and improve the document's 
contents. All comments should be sent to: 

Group Leader 

Emission Factor and Inventory Group (MD-14) 

U. S. Environmental Protection Agency 
Research Triangle Park, North Carolina 27711 


.1-4 




SECTION 2.0 

OVERVIEW OF DOCUMENT CONTENTS 

This section briefly outlines the nature, extent, and format of the material presented in the 
remaining sections of this report. 

Section 3.0 provides a brief summary of the physical and chemical characteristics of 
arsenic and arsenic compounds and an overview of their production, uses, and emission sources. 
This background section is useful in developing a general perspective on arsenic, how it is 
produced and consumed, and identifies potential sources of arsenic emissions. 

Section 4.0 describes various combustion source categories where arsenic emissions have 
been reported. For each type of combustion source, a description(s) of the combustor is given 
and potential arsenic emission points are identified on diagrams. Emission factors for potential 
arsenic emissions, before and after controls, are given where available. 

Section 5.0 focuses on air emissions of arsenic from the metallurgical industry. For each 
major production source category described in Section 5.0, a list of individual companies 
identified in that particular industry is provided. An example process description and a flow 
diagram with potential arsenic emission points are provided. Emission factors for potential 
arsenic emissions, before and after controls employed by industry, are given where available. 

Section 6.0 describes arsenic emissions from the pulp and paper industry. Process 
descriptions, emissions, and associated control techniques from kraft recovery furnaces, smelt 
dissolving tanks, lime kilns, and sulfite recovery furnaces are described. 


. 2-1 


Section 7.0 summarizes other source categories that use arsenic and arsenic compounds 
in their processes and emit arsenic or source categories whose raw materials contain arsenic that 

9 

is emitted in the manufacturing process. The source categories discussed here include the 
production of glass, agricultural chemicals, wood preservers, lead pencils and art goods, prepared 
feeds, and Portland cement. Limited information on many of these sources is available; 
therefore, varying levels of detail on the processes, emissions, and controls are presented. 
Locations of facilities in each source category are provided, where available. 

Section 8.0 summarizes available procedures for source sampling and analysis of arsenic. 
This section provides an overview of applicable sampling procedures and cites references for 
those interested in conducting source tests. 


Appendix A presents a summary table of the emission factors contained in this document. 
This table also presents the factor quality rating and the Source Classification Code (SCC) or 
Area/Mobile Source (AMS) code associated with each emission factor. 


Each emission factor listed in Sections 4.0 through 7.0 was assigned an emission factor 
rating (A. B, C. D. E, or U) based on the criteria for assigning data quality ratings and emission 
factor ratings as required in the document Procedures for preparing Emission Factor 
Documents. 1 The criteria for assigning the data quality ratings to source tests are as follows: 


A - Tests are performed by using an EPA reference test method, or when not 

applicable, a sound methodology. Tests are reported in enough detail for adequate 
validation, and, raw data are provided that can be used to duplicate the emission 
results presented in the report. 

B - Tests are performed by a generally sound methodology, but lacking enough detail 
for adequate validation. Data are insufficient to completely duplicate the emission 
result presented in the report. 

C - Tests are based on an unproven or new methodology, or are lacking a significant 
amount of background information. 

D - Tests are based on generally unacceptable method, but the method may provide an 
order-of-magnitude value for the source. 


2-2 


Once the data quality ratings for the source tests had been assigned, these ratings along 
with the number of source tests available for a given emission point were evaluated. Because of 
the almost impossible task of assigning a meaningful confidence limit to industry-specific 
variables (e.g„ sample size vs. sample population, industry and facility variability, method of 
measurement), the use of a statistical confidence interval for establishing a representative 
emission factor for each source category was not practical. Therefore, some subjective quality 
rating was necessary. The following quality ratings were used in the emission factor tables in 
this document: 

A - Excellent. Emission factor is developed primarily from A- and B-rated source test 
data taken from many randomly chosen facilities in the industry population. The 
source category population is sufficiently specific to minimize variability. 

B - Above average. Emission factor is developed primarily from A- or B-rated test 

data from a moderate number of facilities. Although no specific bias is evident, it 
is not clear if the facilities tested represent a random sample of the industry. As 
with the A rating, the source category population is sufficiently specific to 
minimize variability. 

C - Average. Emission factor is developed primarily from A-, B-, and C-rated test 

data from a reasonable number of facilities. Although no specific bias is evident, 
it is not clear if the facilities tested represent a random sample of the industry. As 
with the A rating, the source category population is sufficiently specific to 
minimize variability. 

D - Below average. Emission factor is developed primarily form A-, B-, and C-rated 
test data from a small number of facilities, and there may be reason to suspect that 
these facilities do not represent a random sample of the industry. There also may 
be evidence of variability within the source population. 

E - Poor. Factor is developed from C- rated and D-rated test data from a very few 
number of facilities, and there may be reasons to suspect that the facilities tested 
do not represent a random sample of the industry. There also may be evidence of 
variability within the source category population. 

U - Unrated (Only used in the L&E documents). Emission factor is developed from 
source tests which have not been thoroughly evaluated, research papers, modeling 
data, or other sources that may lack supporting documentation. The data are not 
necessarily “poor,” but there is not enough information to rate the factors 
according to the rating protocol. 


2-3 


/ 


This document does not contain any discussion of health or other environmental 
effects of arsenic, nor does it include any discussion of ambient air levels. 


2-4 


Tty 

References For Section 2.0 

Procedures for Preparing Emission Factor Documents. EPA-454/R-95-015. Research 
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air 
Quality Planning and Standards, October 1997. 

Factor Information Retrieval (FIRE) System, Version 4.0. Research Triangle Park, North 
Carolina: U.S. Environmental Protection Agency, Office of Air Quality Planning and 
Standards, June 1995. 


o 


2-5 

































. 

‘ 


* . 




■ 



_ 
































tV 


SECTION 3.0 
BACKGROUND 

3.1 Physical And Chemical Nature Of Arsenic And Arsenic Compounds 

Elemental arsenic (As, Chemical Abstract Service [CAS] No. 7440-38-2) is a silver-gray 
crystalline metallic solid that exhibits low thermal conductivity. Although arsenic is often 
referred to as a metal, it is classified chemically as a nonmetal or metalloid belonging to 
Group 15 (VA) of the periodic table. The principal valances of arsenic are +3, +5 and -3. Only 
one stable isotope of arsenic having mass 75 (100 percent natural abundance) has been observed. 
Arsenic typically exists in the (alpha)-crystalline metallic form which is steel-gray in appearance 
and brittle in nature, and in the beta-form, a dark gray amorphous solid. 1 “Metallic” arsenic 
remains stable in dry air, but its surface will oxidize when exposed to humid air, creating a 
superficial golden bronze tarnish that turns black upon prolonged exposure. The physical 
properties of arsenic are presented in Table 3-1. 1 

Arsenic is found widely in nature, most often combined with oxygen, chlorine and sulfur. 
It is found in trace quantities in all living things, the atmosphere, water and geological 
formations." It is usually found in ores containing gold, silver, cobalt, nickel, and antimony. 
There are over 150 known arsenic-bearing minerals. Table 3-2 lists some of the more common 
minerals. 1 The most significant source of commercial arsenic is a byproduct from the treatment 
of copper, lead, cobalt and gold ores. The amount of arsenic found in lead and copper ores may 
range from a trace to 2 to 3 percent. 1 Commercial end uses of arsenic include the following: 
wood preservatives (e.g., chromium copper arsenate); electronics (e.g., semiconductors); 
medicinals and botanicals; agriculture products (e.g., fungicides, herbicides, pesticides, and 
silvicides); desiccants; nonferrous alloys; animal feed additives; glass; ceramics; and dyeing and 


3-1 


TABLE 3-1. PHYSICAL PROPERTIES OF ARSENIC 


Property 

Value 

Atomic weight 

74.92 

Melting point (at 39.1 MPa) a 

816°C 

Boiling point. 

615°C b 

Specific gravity (26°C) 

5,778 kg/m 3 

Specific heat 

24.6 J/(mol-K) c 

Latent heat of fusion 

27,740 J/(mol-K) c 

Latent heat of sublimation 

31,974 J/(mol-K) c 

Linear coefficient of thermal expansion (20°C) 

5.6 pm/(m-°C) 

Electrical resistivity (0°C) 

26 fiQ/cm 

Crystal system 

hexagonal (rhombohedral) 

Lattice constants (26°C, mm) 

a = 0.376 
e = 1.0548 


Source: Reference 1. 

a To convert MPa to psi multiply by 145. 
b Sublimes. 

c To convert to cal/(mol-K) divide by 4.184. 

printing. Inorganic arsenic occurs naturally in many kinds of rocks. It is most commonly found 
with sulfide ores as arsenopyrite 4 Arsenic combined with carbon and hydrogen is classified as 
organic arsenic. Inorganic and organic arsenic compounds are typically white to colorless 
powders that do not evaporate, and have no smell or special taste. Metallic arsenic, which is not 
naturally-occurring, can be extracted from the flue-dust of copper and lead smelters in the form 
of arsenic trioxide or white arsenic, which can then be reduced with charcoal to produce metallic 
arsenic. The elemental, metallic form of arsenic is used as an alloying additive for metals 
(especially lead and copper shot), battery grids, cable sheaths, and boiler tubes. The high-purity 
or semiconductor grade of metallic arsenic is used in the manufacture of electronic products. 

The various classes of inorganic and organic arsenic compounds are discussed below. Table 3-3 


3-2 





TABLE 3-2. IMPORTANT ARSENIC-BEARING MINERALS 


Mineral 

CAS No. 

Arsenic Content, % 

Arsenopyrite (FeAsS) 

1303-18-0 

46 

Lollingite (FeAs 2 ) 

12255-65-1 

73 

Orpiment 

12255-89-9 

61 

Realger 

12044-30-3 

70 

Native Arsenic 

7440-38-2 

90-100 


Source: Reference 1. 


presents a summary of the chemical formulas and end uses of the most commonly used arsenic 

compounds. 5 

3.1.1 Inorganic Compounds 

Arsenic Hydrides 

The primary binary compound of arsenic and hydrogen is arsine (“arsenic hydride”). It is 
the only known hydrogen compound of arsenic. Arsine is a colorless, very poisonous gas that 
exhibits an unpleasant garlic like odor. It is formed when any inorganic arsenic-bearing material 
is brought in contact with zinc and sulfuric acid. It can be accidentally formed by the reaction of 
arsenic impurities in commercial acids stored in metal tanks. Arsine is not particularly stable and 
begins to decompose into its elements below 572°F. In the presence of moisture, light can affect 
the decomposition. Arsine is capable of reducing many substances. For example, it precipitates 
metallic silver from silver nitrate solution. The pure gas is stable at normal temperature. While 
it is not oxidized by air at room temperature, it can be ignited with the formation of arsenic, 
arsenic trioxide, or arsenic pentoxide, depending upon the supply of air. Arsine is used as a 
dopant in the semiconductor industry, 3 and is used to produce gallium arsenide, GaAs, which is 
used in the field of optoelectronic and microwave devices. 


3-3 






TABLE 3-3. COMMON ARSENIC COMPOUNDS 


Compound 

Chemical Formula 
or Description 

Uses 

Arsenic acid 

H 3 AsO 4 -0.5H 2 O 

Manufacture of arsenates, glass making, 
wood treating process, defoliant (regulated), 
desiccant for cotton, soil sterilant. 

Arsenic disulfide 

As 2 S2 

Leather industry, depilatory agent, paint 
pigment, shot manufacture, pyrotechnics, 
rodenticide, taxidermy. 

Arsenic pentafluoride 

AsF 5 

Doping agent in electroconductive polymers. 

Arsenic pentasulfide 

As 2 S 5 

Paint pigments, light filters, other arsenic 
compounds. 

Arsenic pentoxide 

As 2 0 5 

Arsenates, insecticides, dyeing and printing, 
weed killer, colored glass, metal adhesives. 

Arsenic thioarsenate 

As(AsS 4 ) 

Scavenger for certain oxidation catalysts and 
thermal protectant for metal-bonded 
adhesives and coating resins. 

Arsenic tribromide 

AsBr 3 

Analytical chemistry, medicine. 

Arsenic trichloride 

AsCl 3 

Intermediate for organic arsenicals 
(pharmaceuticals, insecticides), ceramics. 

Arsenic trifluoride 

AsF 3 

Fluorinating reagent, catalyst, ion 
implantation source, and dopant. 

Arsenic trioxide 

As-,0 3 

Pigments, ceramic enamels, aniline colors, 
decolorizing agent in glass, insecticide, 
rodenticide, herbicide, sheep and cattle dip, 
hide preservative, preparation of other 
arsenic compounds. 

Arsenic tnsulfide 

As 2 S 3 

Pigment, reducing agent, pyrotechnics, glass 
used for infrared lenses, semiconductors, 
hair removal from hides. 

Arsenic hydride (arsine) 

AsH 3 

Organic synthesis, military poison, doping 
agent for solid-state electronic compounds. 


Source: Reference 5. 


3-4 







Other Arsenic Hydrides 


In general, arsenides have little commercial uses. While some arsenides have a defined 
composition, others are mixtures. Many arsenides occur in nature, and some of the naturally 
occurring arsenides include Cu 3 As (domeykite), FeAs 2 (lollingite), NiAs 2 (chloanthite), NiAs 
(niccolite), and CoAs 2 (smaltite). Diarsine, As 2 H, is a byproduct that occurs from the 
preparation of arsine by treatment of a magnesium aluminum arsenide alloy with dilute sulfuric 
acid. It can also occur by passing arsine at low pressure through an ozonizer-type discharge tube. 
As a gas, diarsine is fairly stable, but rather unstable in condensed phases. 

Arsenic Halides 

While arsenic forms a complete series of trihalides, only arsenic pentafluoride is a 
well-known pentahalide. Table 3-4 lists some known arsenic halides. 1 All of the arsenic halides 
are covalent compounds that hydrolyze in water 1 and can be formed by direct combination of the 
elements. Arsenic trichloride is the most common and commercially significant of all arsenic 
halides. W T ith a low boiling point, it is easily separated from tin trichloride and the chlorides of 
other metals. It can also be formed by spontaneous combustion of the elements. Arsenic 
trichloride has been used as a starting material for the production of numerous organoarsenic 
compounds and for the preparation of chlorine derivatives of the arsines. In addition, it is used as 
a dopant in the semiconductor industry and in the production of high-purity arsenic metal. Other 
arsenic halides include arsenic trifluoride, arsenic pentafluoride, arsenic pentachloride, arsenic 
tribromide, arsenic tniodide, and arsenic diiodide. 

Arsenic Oxides and Acids 

The only arsenic oxides that are commercially significant are the trioxide and pentoxide. 
Arsenic trioxide and arsenic pentoxide are described in detail below. 


3-5 


TABLE 3-4. PHYSICAL PROPERTIES OF ARSENIC HALIDES 



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3-6 









Arsenic Trioxide —Arsenic trioxide is also known as white arsenic. It is the most 
commercially important arsenic compound. It can occur in two different crystalline forms and 
one amorphous variety. The octahedral or cubic modification, arseiiolite, is the most common 
form and is stable at room temperature. It changes into a monoclonic modification, claudetite 
(consisting of sheets of AS0 3 pyramids sharing oxygen), at temperatures above 430°F. This 
modification is formed when condensation occurs at temperatures above 430°F. Condensation 
above 482 °F will generally form the amorphous, glassy phase which devitrifies into the 
octahedral modification at room temperature. This octahedral variety is a white solid that 
sublimes above 275°F and melts at 527°F under its own vapor pressure. 1 

Arsenic trioxide slightly dissolves in water to form a weakly acidic solution. It is soluble 
in acids and bases (amphoteric). It can be made by burning arsenic in air, or by the hydrolysis of 
an arsenic trihalide. Commercially, it is prepared by roasting arsenopyrite. It is often used as a 
primary analytical standard in oxidimetry since it is readily attainable in a high state of purity and 
is quantitatively oxidized by many reagents commonly used in volumetric analysis 
(e.g.. dichromate, nitric acid, hypochlorite, and iron(DI)). 

Arsenic Pentoxide — Arsenic pentoxide is a “white glassy mass,” made up of equal 
numbers of octahedra and tetrahedra sharing comer oxygens to give cross-linked strands. 3 It is 
an oxidizing agent capable of liberating chlorine from hydrogen chloride. The compound 
deliquesces in air to form arsenic acid. It dissolves in water slowly, is thermally unstable, and 
begins to decompose near the melting point, around 572°F. The vapor is made up of arsenic 
trioxide and oxygen. The pentoxide can be made by reacting arsenic trioxide with oxygen under 
pressure, or by dehydration of crystalline arsenic acid at temperatures above 392°F (the best 
method). 1 

Arsenous Acid —Arsenous acid is a weak acid with a dissociation constant of 8xl0* 16 at 
77°F. It is known to exist only in solution. 

Arsenic Acid —Arsenic acid, is known in the solid state as the hemihydrate 
H 3 AsO 4 -0.5H o O and occurs as rhombic, deliquescent crystals. It is made by the oxidation of 


.3-7 






arsenic trioxide with concentrated nitric acid. Arsenic acid will lose water upon heating to 248 °F 
and forms pyroarsenic acid. At elevated temperatures, more water is lost and meta-arsenic acid 
forms. In an acidic solution, arsenic acid and its salts are strong oxidizing agents. Arsenic acid 
is used as a defoliant and as a starting material for important inorganic and organic arsenic 
compounds. 3 Various salts (arsenates) are derived from arsenic acid, and are described in detail 
below. 

Arsenates 

Arsenates are oxidizing agents and are reduced with concentrated hydrochloric acid or 
sulfur dioxide. They are generally similar to the phosphates in their compositions and 
solubilities. Of the many salts of arsenic acid, the salts of potassium, sodium, calcium and lead 
are important commercially. Arsenates of calcium or lead are often used as insecticides. When a 
solution of ortho-arsenate is treated with silver nitrate in neutral solution, a chocolate-brown 
precipitate of silver ortho-arsenate forms. Silver ortho-arsenate can be used as a test to 
distinguish arsenates from phosphates. With hydrofluoric acid, ortho-arsenate solutions yield 
hexafluoroarsenates (e.g., potassium hexafluoroarsenate). 

Arsenic Sulfides 

Table 3-5 presents the physical properties of the common arsenic sulfides. 1,3 These 
arsenic sulfides are described in detail below. 

Arsenic Disulfide -Arsenic disulfide (“red glass”) exists in ruby-red crystals or as an 
amorphous reddish mass. It occurs naturally as the mineral realger. At 513 °F it changes into a 
black allotropic modification and at 585°F the compound melts. Its purity and fineness rather 
than its chemical composition determine its commercial value. Industrially manufactured red 
arsenic glass varies in its composition. Today, red glasses typically contain around 61 to 
64 percent arsenic and 39 to 36 percent sulfur. Commercially, the compound is produced by 
heating a mixture of iron pyrites and arsenopyrites or by heating arsenic trioxide with sulfur. It 
can also be made by prolonged treatment of arsenous sulfide with boiling aqueous sodium 


3-8 



TABLE 3-5. PHYSICAL PROPERTIES OF COMMON ARSENIC SULFIDES 


Arsenic Sulfides 

CAS No. 

Molecular 

Formula 

Color and Physical 
State at 25 °C 

Arsenous sulfide (orpiment) 

12255-89-9 

As 2 S 3 - . 

Yellow solid 

Arsenic sulfide (realgar) 

12279-90-2 

As 4 S 4 

Gold or orange solid 

Arsenic pentasulfide 

1303-34-0 

As 4 S 10 

Yellow solid 

Tetraarsenic trisulfide 

1303-41-9 

AS 4 S 3 

Orange-yellow 

Tetraarsenic pentasulfide 

25114-28-7 

As 4 S^ 



Source: Reference 1. 


bicarbonate, or by heating a sodium bicarbonate-arsenous sulfide mixture in a sealed tube. Water 
does not affect it, however it will oxidize in nitric acid and inflame in chlorine. Red glass is 
primarily used as a depilatory in the manufacture of fine leather, and also used in pyrotechnics. 

Arsenic (TIT) Sulfide -Arsenic (III) sulfide is known as orpiment and occurs as a yellow 
mineral. It is made by precipitation of trivalent arsenic compounds with hydrogen sulfide. The 
colloidal solution of the arsenic trisulfide can be flocculated with hydrochloric acid, in which it is 
insoluble. It readily dissolves in basic reagents. Orpiment contains unchanged arsenic trioxide 
and is poisonous. It was used in the past for cosmetic purposes, but currently it is used in the 
semiconductor industry, in the production of infrared-permeable windows, and as a pigment. 

Arsenic (V) Sulfide -Arsenic (V) sulfide (also referred to as arsenic pentasulfide) is made 
by fusing stoichiometric quantities of arsenic and sulfur powder or by precipitation from highly 
acidic arsenate (V) solution with H 2 S. Arsenic (V) sulfide will decompose into arsenic (III) 
sulfide and sulfur. The compound is stable in air up to temperatures of 203 °F, but begins to 
dissociate into arsenous sulfide and sulfur at higher temperatures. It can be hydrolyzed by 
boiling with water resulting in arsenous acid and sulfur. 


3-9 









3.1.2 Organic Arsenic Compounds 


Arsenic combines easily with carbon to form a wide variety of organic compounds with 
one or more As-C bonds. There are many known organoarsenic compounds. Table 3-6 presents 
a number of examples . 1 

Arsenic compounds used in agriculture as plant protection agents and pesticides have 
largely been replaced by metal-free compounds. In the United States, only certain preparations 
are allowed for use in some States (e.g., those of the Ansar series). For wood preservatives, 
arsenic compounds are used solely in compound preparations. Organic arsenic compounds can 
be grouped into aliphatic organoarsenic compounds and aromatic organoarsenic compounds. 
Both of these groups are described in detail below. 

Aliphatic Organoarsenic Compounds 

This class of compounds is still used as herbicides and fungicides in rice, cotton, fruit, 
and coffee plantations, particularly in Eastern Asia. The three main aliphatic organoarsenic 
compounds are described below. 

Methanearsonic Acid 

Salts of methanearsonic acid, particularly the iron ammonium salt, Neoasozin, are used as 
a fungicide in rice growing. The sodium, ammonium, and diethanolammonium salts are used as 
herbicides in cotton growing. 3 

Dimethylarsinic acid 

Dimethylarsinic acid, also called Ansar 160, is used as a total herbicide and desiccant. 
Generally, it is produced by reaction of methyl halide with a salt of arsenous acid. 3 


3-10 


TABLE 3-6. ORGANIC ARSENIC COMPOUNDS 


Compound 

CAS Number 

Molecular 

Formula 

Ethylarsine 

' ‘ 593-59-9 

C 2 H 7 As 

Diethylarsine 

692-42-2 

C 5 H n As 

Triphenylarsine 

603-32-7 

C, 8 Hi 5 As 

Dimethylbromoarsine 

676-71-1 

C 2 H 6 AsBr 

Methyldifluoroarsine 

420-24-6 

CH 3 AsF 

Oxophenylarsine 

637-03-6 

C 6 H 5 AsO 

Phenylarsonous acid 

25400-22-0 

C 6 H 7 As0 2 

Dimethylarsinous cyanide 

683-45-4 

C 3 H 6 AsN 

Methyl diphenylarsinite 

24582-54-5 

C 13 H 13 AsO 

Tetrakis(trifluoromethyl) diarsine 

360-56-5 

C 4 As 2 F 12 

Pentamethylpentaarsolane 

20550-47-4 

C 5 H 15 As 5 

4-Ethvlarsenin 

76782-94-0 

C 7 H 9 As 

1 -Chloroarsolane 

30077-24-8 

C 4 H 8 AsO 

l//-arsole 

4542-21-6 

C 4 H 5 As 

Phenylarsonic acid 

98-05-5 

C 6 H 7 As0 3 

Diphenylarsinic acid 

4656-80-8 

C^H] jAs0 2 

Arsonoacetic acid 

107-38-0 

C 2 H 5 As0 5 

Diethyl methylarsonate 

14806-25-8 

C^H^AsC^ 

Triphenylarsine oxide 

1153-05-5 

^18^15^0 

Tetrachlorophenylarsorane 

29181-03-1 

^HjAsC^ 

Tetramethylarsonium perchlorate 

84742-76-7 

C 4 H 12 AsC10 4 

Triphenvlarsonium 2-propenylide 

88329-28-6 

_C 2 iHi 9 As_ 


Source: Reference 1. 


3-11 







Aromatic Organoarsenic Compounds 


There are two classic methods of preparing aromatic organoarsenic compounds. In one 
method, aniline is reacted with arsenic acid at 392 °F as seen in the sulfonation of organic 
compounds: 

C 6 H 5 NH 2 + H 3 As0 4 -> H 2 N + C 6 H 4 + AsO(OH) 2 

In the other method, diazo compounds are reacted with sodium arsenate (IH): 

C 2 H 5 N 2 C1 + Na 3 As0 3 ~> C 6 H 5 + AsO(ONa) 2 + N 2 + NaCl 

Of the two methods, the second method has proven to be the most commercially 
important in producing arsonic acids. 

In a more modem process, arsenic acid complexed with EDTA is added at 266°F to a 
solution of excess aniline in perchloroethylene. The water of reaction and any unreacted aniline 
are separated off, and the bis(4-aminophenyl)arsinic acid intermediate is converted by acidic 
hydrolysis into arsanilic acid. 

Arsonic acids are used in various industrial applications. For example, they have been 
used as corrosion inhibitors for iron and steel, and as additives for motor fuel, agricultural 
bactericides, herbicides, and fungicides. 

The primary use of the arsonic acids was in their supplementary processing to 
arsenobenzenes and “arsenic oxides” by reduction with S0 2 , phosphorus trichloride, sodium 
dithionite, phosphorous acid, or tin (II) chloride. Reduction with zinc dust and hydrochloric acid 
yields the arsines, which are reoxidized in air (e.g., phenylarsine, rapidly oxidized in air to form 
the arseno compound, C 6 H 5 As n ). Additional uptake of oxygen is considerably slower unless 
catalyzed (e.g., by iron). 3 


3-12 


Arsenic oxides are relatively stable. All arsenic oxide compounds are oxidized to arsonic 
derivatives by strong oxidants, including hydrogen peroxide, halogens, and Chloramine—T 
(sodium p-toluenechlorosulfonamide). 

V f 

The aromatic arsonic acids are dibasic. Aqueous solutions of the monosodium salts are 
neutral to mildly acidic, whereas those of the disodium salts are slightly alkaline (pH of 8 to 9). 
Magnesium and calcium salts are typically soluble in cold water, but upon heating, they 
precipitate to practically insoluble deposits. Because magnesium and calcium salts are soluble in 
cold water, they can be used to separate arsonic salts from cold solutions. Arsonic acids 
generally crystallize well, and their stability depends on the substituents on the benzene ring. 
Some form azo dyes that contain both arsonic acid and sulfonic acid groups, and are used in the 
analysis of metals. 

Aromatic Arsenobenzenes 

Aromatic arseno compounds have amino or hydroxyl groups and are soluble in acids and 
alkalis. Aromatic arseno compounds will become soluble in water with the addition of a 
formaldehyde sulfoxylate or formaldehyde hydrogen sulfite into the amino group. 

Organic Oxoarsenic Compounds (“Arsenic Oxides”) 

The reduction of organoarsenic compounds can be controlled by using an appropriate 
reducing agent so that reaction terminates at the preferred intermediate stage. However, this does 
not occur with oxidation. In the most commonly used method for the production of organic 
oxoarsenic compounds from arsonic acids, the acid is directly reduced to the anhydride of the 
arsonous acid with S0 2 . 

Organic oxoarsenic compounds are the anhydrides of the arsonous acids. They are 
extremely poisonous, amphoteric substances barely soluble in water. When dissolved in acids 

and alkalis, they form salts and can be precipitated from those solutions by carbon dioxide or 

• t 3 

ammonium chloride. 


3-13 


3.2 Fate Of Arsenic 


As previously stated, arsenic is ubiquitous, and is emitted naturally from many sources 
(e.g., volcanoes, forest wild fires, erosion from mineral deposits). However, the releases 
originating from human activities (e.g., metal smelting, chemical production and use, coal 
combustion, waste disposal, pesticide application) are the emissions that can cause substantial 
environmental contamination. The greatest environmental concentrations of arsenic have been 
observed in air and soil around mining and smelter operations, whereas coal combustion 
distributes arsenic to the air in much lower concentrations over a wider area. A brief discussion 
of the fate of arsenic upon being released to the air, water, and soil is provided below. 

3.2.1 Fate of Arsenic in Soil 

The majority of soils naturally contain low levels of arsenic (1 to 5 ppm) but certain 
industrial wastes and pesticide applications can increase concentrations. Approximately 
80 percent of the total amount of arsenic that is released to the environment from anthropogenic 
activities is released to soil. 6 The major anthropogenic sources contributing to arsenic in soils 
include the application of pesticides and disposal of solid wastes from fossil fuel combustion and 
industrial processes. Organoarsenical pesticides (e.g., monosodium methanearsonate, disodium 
methanearsonate) applied to soils are metabolized by soil bacteria to form alkylarsines and 
arsenate. 7,8 

Land application of sewage sludge has proven to be another source of arsenic in soil. 
While arsenic has been observed in soil at various hazardous waste sites, it is not always obvious 
that it was a result of the waste site or from natural causes. 

Regardless of the source or form of arsenical, arsenic will react with soil components. 

The predominant reaction is adsorption onto and reaction with hydrous iron and aluminum 
oxides which coat soil particles. Heavier soils with a higher clay content and hydrous oxide 
content adsorb more arsenic than do lighter sandier soils with low clay content. 8 In addition, 
arsenicals react with ions in solution, such as iron, aluminum, calcium, and magnesium, but may 


3-14 


• 2 V 

also include manganese and lead. Each ion detaches a part of the arsenical depending on the 
solubility of the compound and the quantity of reactants present. Hence, a soil may be saturated 
relative to some compounds and not others. The pH of the soil will affect the solubility of these 
compounds; therefore, changing the soil pH may affect each arsenical’s solubility. 

There are two known types of oxidation that are responsible for transforming arsenicals 
environmentally. One type destroys the carbon/arsenic bond and is associated with microbial 
activity, while the other type causes a change in oxidation state which may or may not be affected 
by microbial activity. Transformations of arsenic in soil are similar to those seen in aquatic 
systems, with As +5 predominant in aerobic soils; As +3 in slightly reduced soils (e.g., temporarily 
flooded); and arsine, methylated arsenic, and elemental arsenic in very reduced conditions 
(e.g., swamps and bogs). 6,8 Some arsenate may be reduced to arsenite under certain 
environmental conditions. Arsenic in sediments or in flooded anaerobic soil may be reduced as a 
function of reduction/oxidation potential. 

3.2.2 Fate of Arsenic in Water 

Arsenic can be found in surface water, groundwater, and finished drinking water 
throughout the United States. The majority of arsenic in natural water is a mixture of arsenate 
and arsenite, with arsenate usually predominating. 8 

Arsenic is released to water in several ways, including natural weathering processes, 
discharge from industrial facilities, and leaching from landfills, soil or urban runoff. Once in 
water, arsenic can go through a complex series of transformations, including oxidation-reduction 
reactions, ligand exchange, and biotransformations. The factors that most strongly influence the 
transformations that arsenic will undergo are the oxidation-reduction potential (Eh), pH, metal 
sulfide and sulfide ion concentrations, iron concentrations, temperature, salinity, and distribution 
and composition of the biota. 8 Arsenate is usually the predominant form of arsenic in water, 
however, aquatic microorganisms may reduce the arsenate to arsenite and a variety of methylated 
arsenicals. 


3-15 


Once in water, the transport and partitioning of arsenic will depend upon its chemical 
form as well as interactions with other materials present. Any soluble forms will move with the 
water, and can be carried long distances through rivers. However, arsenic can also be adsorbed 
from water onto sediments and soils, particularly clays, iron oxides, aluminum hydroxides, 
manganese compounds, and organic material. 8 Once in sediments, arsenic can be released back 
into the water through chemical and biological interconversions of arsenic species. 

3.2.3 Fate of Arsenic in Air 

Arsenic can be released to air from natural sources (e.g., volcanoes and forest fires) and 
from various industrial sources (e.g., coal combustion, smelter and mining activities) and 
pesticide application. Arsenic in air primarily exists in the form of particulate matter (mostly in 
panicles less than 2 pm in diameter) and is usually a mixture of arsenite and arsenate. These 
panicles can be transported by wind and air currents until they are brought back to earth by wet 
or dry deposition. The residence time of arsenic bound to particulate depends on particle size 
and meteorological conditions; however, a typical value is approximately 9 days. 8 As might be 
expected, levels of arsenic in air vary with distance from the source, height of the stack, and wind 
speed. In general, large cities have higher levels of arsenic air concentrations than smaller ones. 
This is probably due to emissions from coal powered plants. In addition, areas that are near 
nonfenous metal smelters have reported extremely high arsenic air concentrations (up to 
1.56x10' 10 lb/ft 3 ). 8 

3.2.4 Fate of Arsenic in Plants and Food 

Once arsenic enters the environment, it enters the food chain. Bioconcentration of arsenic 
occurs in aquatic organisms, mainly in algae and lower invertebrates. Low levels of arsenic have 
been measured in freshwater invertebrates and fish, while higher levels have been observed in 
marine oysters. Apparently, biomagnification in aquatic food chains is not significant, although 
some fish and invertebrates have high levels of arsenic compounds. 


3-16 


Once arsenic is in the soil, it can be taken into plants via root uptake (plants can also 
obtain arsenic through foliar absorption). In general, the greater the amount of arsenic available 
for uptake, the greater the amount that will be absorbed by a plant. However, available arsenic is 
not proportional to total arsenic. A low (10 to 50 ppm) arsenic content in a sandy soil may be 
more phytotoxic (i.e., available) than much higher levels (200 to 500 ppm) in a heavier clay soil 
and, therefore, a plant grown on sandy soil will contain higher residue levels. 8 

3.3 Overview Of Production And Use 

Commercial arsenic is primarily produced as a by-product in the smelting of nonferrous 
metal ores containing gold, silver, lead, nickel, and cobalt. In 1985, all United States domestic 
production of arsenic ceased. 

■H 

At the present time, approximately 17 countries (the U.S. is not included) recover arsenic 
as arsenic trioxide from the smelting or roasting of nonferrous metal ores or concentrates. 
According to the U.S. Bureau of Mines, in 1993, the United States imported all of the arsenic it 
required (almost 13,228 tons). Table 3-7 presents U.S. import data for arsenicals from 1991 
to 1993 by country. 9 About 97 percent was imported as arsenic trioxide, and approximately 
3 percent as metallic arsenic. 9 China, the world’s largest producer of both arsenic trioxide and 
metallic arsenic, sold large amounts of both commodities to the United States. 

Historically, arsenic was used in agricultural applications as an insecticide, herbicide, and 
cotton desiccant. However, with an increase in environmental awareness and a better 
understanding of the toxicity of arsenic, most of the agricultural uses for arsenic were banned. 
Around 1975, the use of arsenic as a wood preservative began to grow and by 1990, 70 percent of 
arsenic consumed in the United States was used by the wood preservative industry and 
20 percent by the agricultural industry. 10 The primary use of arsenic in the United States today is 
in the manufacture of chemicals, with arsenic trioxide being the sole starting material. 3 Metallic 
arsenic has a limited demand but still finds use in electronic and semiconductor applications. 

The production and uses of both metallic arsenic and arsenic trioxide are presented below. 


3-17 


TABLE 3-7. U.S. IMPORTS FOR CONSUMPTION OF ARSENICALS, BY COUNTRY 


Class 

Country 

1993 Quantity (tons) 

Arsenic trioxide 

Australia 

— 


Belgium 

747 


Chile 

6,670 


China 

12,908 


Finland 



France 

2,080 


Germany 

17 

. 

Ghana 

— 


Hong Kong 

1,813 


Mexico 

4,304 


Philippines 

1,267 


South Africa, Republic of 

132 


Sweden 

— 


Taiwan 

— 


United Kingdom 

19 


Other 

389 


Total 

30,346 

Arsenic Metal 

Belgium 

— 


Canada 

a 


China 

762 


Germany 

12 


Hong Kong 

19 


Japan 

52 


Philippines 

— 


United Kingdom 

1 


Tota! b 

845 


Source: Reference 9. 
a Less than 1/2 unit. 

b Data may not add to totals shown because of independent rounding. 


3-18 







3.3.1 Metallic Arsenic 


Metallic arsenic is mainly used in nonferrous alloys. Small amounts (around 0.5 percent) 

of arsenic are added to lead-antimony grid alloys used in lead^acid batteries to increase endurance 

# * 

and corrosion resistance. Additions of the same order (0.02 to 0.5 percent) to copper alloys raise 
the recrystallization temperature and improve high temperature stability and corrosion resistance. 
Additions of arsenic (up to 2 percent) to lead in shot improve the sphericity of lead ammunition. 
While limited, there is a demand for high-purity arsenic (99.99 percent and greater) for use in the 
semiconductor and electronics industry. It is used in electronics together with gallium or indium 
for producing light emitting diodes (LED), infrared detectors, and lasers. High-purity metallic 
arsenic is used in the production of photoreceptor alloys for xerographic plain paper copiers. 1 In 
the past (1974 to 1986), arsenic was supplied domestically by ASARCO, Inc., which shut down 
its operation due to economic and environmental pressures. The United States must now rely 
upon imports from Japan, Canada, and the United Kingdom for its high purity metallic arsenic. 
Metallic arsenic may also be used in condensers, evaporators, ferrules, and heat exchanger and 
distillation tubes. 1 

3.3.2 Arsenic Trioxide 

Arsenic trioxide is easily volatilized during the smelting of copper and lead concentrates, 
and is therefore concentrated with the flue dust. 1 Most of this raw material originates from 
copper smelters, although some also comes from lead, cobalt, and other smelters. Crude flue 
dust may contain up to 30 percent arsenic trioxide, the balance being oxides of copper or lead, 
and other metals such as antimony. This crude flue dust is subsequently upgraded by mixing 
with a small quantity of pyrite or galena and roasting. Pyrite and galena are added to prevent 
arsemtes from forming during roasting. 1 During roasting, the gases and vapors are allowed to 
pass through a cooling flue which consists of a series of brick chambers or rooms called kitchens. 
The arsenic vapor which condenses in these chambers is of varying purity (from 90 to 
95 percent). 1 Higher purity products can be obtained by resubliming the crude trioxide, an 
operation typically carried out in a reverberatory furnace. 


3-19 


Since arsenic trioxide is a by-product, production is not based on the demand for arsenic 
but by the demand for copper, lead, etc. 3 The biggest consumers of arsenic trioxide are the 
United States, Malaysia and the United Kingdom. 3 Until the late 1980s, the United States was 
the main supplier of arsenic trioxide for domestic use. Now it must rely entirely on imports. 

Most arsenic is used in the form of compounds with arsenic trioxide as the sole starting 
material. Arsenic trioxide is the primary commodity of commerce from which a number of 
important chemicals are manufactured. 

Refined arsenic trioxide, once used as a decolorizer and fining agent in the manufacturing 
of bottleglass and other types of glassware, is being replaced by arsenic acid for environmental 
reasons. Arsenic acid is used in the preparation of wood preservative salts, primarily chrome 
copper arsenate. Arsenilic acid is used as a feed additive for poultry and swine. Sodium arsenite 
is useful for cattle and sheep dips. 


3-20 


1 . 


■w - 

References For Section 3.0 

Kirk-Othmer Encyclopedia of Chemical Technology. 4th Edition, Volume 3. New York, 
New York: John Wiley and Sons, Inc., 1992. pp. 624-659. 

2 Lederer, W.H. and R.J. Fensterheim (eds). Arsenic: Industrial, Biomedical, 

Environmental Perspectives. New York, New York: Van Nostrand Reinhold, 1983. 

3. Hanusch, K., H. Grossman, K.A. Herbst, B. Rose, and H.V. Wolf. Arsenic and Arsenic 
Compounds. In: Ullman's Encyclopedia of Industrial Chemistry. 5th ed. .Volume A3. 
W. Gerhartz, Y.S. Yamamoto, F.T. Campbell, R. Pfefferkom, J.F. Rounsaville, eds. 
Federal Republic of Germany: VCH, 1985. pp. 113-141. 

4. U.S. EPA. Clean Air Act, Section 112(h) Candidate Pollutants , draft report. Research 
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air 
Quality Planning and Standards, Visibility and Ecosystem Protection Group, 1996. 

5. Hawley's Condensed Chemical Dictionary, 12th ed. R.J. Lewis, Sr., ed. New York, New 
York: Van Nostrand Reinhold, 1993. 

6. U.S. EPA. Arsenic. In: Intermedia Priority Pollutant Guidance Documents. 
Washington. D.C.: U.S. Environmental Protection Agency, Office of Pesticides and 
Toxic Substances, 1982. 

7. Hood, R.D. Cacodylic Acid: Agricultural Uses, Biological Effects, and Environmental 
Fate. Report to Veterans Administration Central Office, Agent Orange Projects Office, 
Washington, D.C., by the University of Alabama, Tuscaloosa, Alabama, and R.D. Hood 
and Associates, Northport, Alabama, 1985. 

8. U.S. Department of Health and Human Resources. Toxicological Profile for Arsenic, 
Draft Update. Public Health Service. Agency for Toxic Substances and Disease 
Registry, February 18, 1992. 

9. U.S. Department of Interior. Mineral Industry Surveys - Arsenic in 1993. Washington, 
D.C.: U.S. Department of Interior, Bureau of Mines, June 22, 1994. 

10. Loebenstein, J.R. The Materials Flow of Arsenic in the United States. Washington, 

D.C.: U.S. Department of Interior, Bureau of Mines, 1994. pp. 1-12. 


3-21 

























■ 




■ 








' 

wmm 

. 

. 

- 

























































I EE ■ 




















. 




■ 






- 




■ 

. 




■ 















■ 


































SECTION 4.0 

EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM 

COMBUSTION SOURCES 


This section contains process descriptions, available emission factor data, and source 
locations for source categories that emit arsenic and arsenic compounds during combustion. 

These source categories include fuel combustion in stationary external combustion, incineration 
of various types of waste, including municipal waste, sewage sludge, medical waste, hazardous 
waste, as well as internal combustion, kraft pulping lime kilns, and crematories. 

There are few emission controls that are dedicated solely to reducing arsenic emissions 
from combustion sources. However, the control strategies used to reduce particulate matter (PM) 
in general have been found to be effective in controlling arsenic emissions in particulate form. 
Where a specific emission control strategy has been identified to reduce arsenic emissions from a 
particular combustion source discussed in this section, that control strategy is discussed as part of 
the process description for that source. In many cases throughout this section, emission factor 
data are provided for both controlled and uncontrolled combustion units that are typically found 
in a particular source category. 

4.1 Stationary External Combustion 

The combustion of solid, liquid, and gaseous fuels such as coal, wood, fuel oil, and 
natural gas has been shown to be a source of arsenic emissions. Arsenic emission rates depend 
on both fuel characteristics and combustion process characteristics. Emissions of arsenic 
originate from arsenic compounds contained in fuels and emitted during combustion. 1,2 Because 
metals such as arsenic only change forms (chemical and physical states) and are never destroyed 
during combustion, the amount of arsenic in the original fuel or waste will be the amount of 


AA 


arsenic found in the ash or emitted from stacks controlled by air pollution control devices 
(APCDs). 3 ' 4 

Arsenic concentration in coal depends on the type of coal. Some specific arsenic 
concentrations in coal are as follows: anthracite coal contains approximately 8 ppm arsenic; 
bituminous coal contains 20 ppm arsenic; subbituminous coal contains 6 ppm arsenic; and lignite 
coal contains 23 ppm arsenic. 5 . 

Arsenic and arsenic compound emissions may be reduced from combustion sources by 
using PM control devices and lower combustion and APCD temperatures. These arsenic 
reduction techniques are discussed briefly below. 

In general, use of PM control devices in combustion/air pollution control systems can be 
viewed as a surrogate for controlling emissions of arsenic and other metals. 4 The most effective 
means of controlling arsenic emissions to the atmosphere are: (1) minimizing arsenic 
vaporization in the combustion zone and (2) maximizing small particle collection in the APCD. 
Arsenic compounds, like many heavy metal compounds, vaporize at elevated temperatures and, 
as temperatures drop, only a fraction of the vaporized metal condenses. The remaining vaporized 
metal can escape through the PM APCD uncontrolled. 

During the combustion process, many trace metals (including arsenic) volatilize and then, 
upon cooling, condense on all available particulate surface area. These submicrometer particles 
with very high surface areas can carry a very high concentration of condensed metal. This 
phenomenon is known as “fine particle enrichment.’’ There are three general factors favoring 
fine panicle enrichment of metals: 4 

• Small panicle size; 

• Large number of particles; and 

• Low flue gas temperatures. 


4-2 


There is some evidence that fine particle enrichment of metals on PM is not as prevalent 
at higher flue gas temperatures. It is believed that as long as the flue gas temperatures remain 
high, the metals tend to remain volatized, such that they do not condense and bond with PM. 4 

The primary stationary combustion sources emitting arsenic compounds are boilers, 
furnaces, heaters, stoves, and fireplaces used to generate heat and/or power in the residential, 
utility, industrial, and commercial use sectors. A description of combustion sources, typical 
emission control equipment, and arsenic emission factors for each of these major use sectors is 
provided in the sections that follow. 

4.1.1 Process Descriptions for Utility, Industrial, and Commercial Fuel Combustion 

Utility Sector 

Utility boilers bum coal, oil, natural gas, and wood to generate steam for electricity 
generation. Fossil fuel-fired utility boilers comprise about 72 percent (or 497,000 megawatts 
[MW]) of the generating capacity of U.S. electric power plants. Of these fuels, coal is the most 
widely used, accounting for approximately 60 percent of the U.S. fossil fuel-powered electricity 
generating capacity. Natural gas represents about 25 percent and oil represents the remaining 
15 percent. 6 

A utility boiler consists of several major subassemblies, as shown in Figure 4-1. 6 These 
subassemblies include the fuel preparation system, air supply system, burners, the furnace, and 
the convective heat transfer system. The fuel preparation system, air supply, and burners are 
primarily involved in converting fuel into thermal energy in the form of hot combustion gases. 
The last two subassemblies transfer the thermal energy in the combustion gases to the 
superheated steam that operates the steam turbine and produces electricity. 6 

Utility boilers are generally identified by their furnace configuration. Different furnace 
configurations used in utility boilers include tangentially-fired, wall-fired, cyclone-fired, 


4-3 


Suparttaatars and Rahaatars 



Flue Gas 


Air 


Figure 4-1. Simplified Boiler Schematic 

Source: Reference 6. 


.4-4 


ERG_POM_4121 pr* 



















































stoker-fired, and fluidized bed combustion (FBC) boilers. Some of these furnace configurations 
are designed primarily for coal combustion, while others are-also used for oil or natural gas 
combustion. The furnace types most commonly used for firing oil and natural gas are the 
tangentially-fired and wall-fired boiler designs. 7 Each of these furnace types is described below. 

Tangentiallv-fired Boiler --The tangentially-fired boiler is based on the concept of a single 
flame zone within the furnace. The fuel-air mixture in a tangentially-fired boiler projects from 
the four comers of the furnace along a line tangential to an imaginary cylinder located along the 
furnace centerline. When coal is used as the fuel, the coal is pulverized in a mill to the 
consistency of talcum powder (i.e., so that at least 70 percent of the particles will pass through a 
200 mesh sieve), entrained in primary air, and fired in suspension. 8 As fuel and air are fed to the 
burners, a rotating “fireball” is formed. By tilting the fuel-air nozzle assembly, this “fireball” can 
be moved up and down to control the furnace exit gas temperature and to provide steam 
temperature control during variations in load. Tangentially-fired boilers commonly bum 
pulverized coal. However, oil or gas may also be burned. 6 

Wall-fired Boiler — The wall-fired boiler, or normal-fired boiler, is characterized by 
multiple, individual burners located on a single wall or on opposing walls of the furnace 
(Figure 4-2). 6 As with tangentially-fired boilers, when coal is used as the fuel it is pulverized, 
entrained in primary air, and fired in suspension. In contrast to tangentially-fired boilers that 
produce a single flame zone, each of the burners in a wall-fired boiler has a relatively distinct 
flame zone. Various wall-fired boiler types exist, including single-wall, opposed-wall, cell, 
vertical, arch, and turbo. Wall-fired boilers may bum pulverized coal, oil, or natural gas. 6 

Cvclone-fired Boiler --In the cyclone-fired boiler, fuel and air are burned in horizontal, 
cylindrical chambers, producing a spinning, high-temperature flame. Cyclone-fired boilers are 
almost exclusively crushed coal-fired. The coal is crushed to a 4-mesh size and admitted with 
the primary' air in a tangential fashion. The finer coal particles are burned in suspension, while 
the coarser particles are thrown to the walls by centrifugal force. 7 Some units are also able to fire 
oil and natural gas. 6 


4-5 







Burner B 
Burner A 


Burner D 
Burner C 


Figure 4-2. Single Wall-Fired Boiler 


Source: Reference 6. 


4-6 


ERO_POM_4122 pr« 

























































































































Fluidized Bed Combustion Boiler -Fluidized bed combustion is a newer boiler 
technology that is not as widely used as the other, more conventional boiler types. In a typical 
FBC, crushed coal in combination with inert material (sand, silica, alumina, or ash) and/or 
sorbent (limestone) are maintained in a highly turbulent suspended state by the upward flow of 
primary air (Figure 4-3). This fluidized state promotes uniform and efficient combustion at 
lower furnace temperatures, between 1,575 and 1,650°F, compared to 2,500 and 2,800°F for 
conventional coal-fired boilers. Fluidized bed combustors have been developed to operate at 
both atmospheric and pressurized conditions. 6 

Stoker-fired Boiler —Instead of firing coal in suspension as in the boilers described above, 
the mechanical stoker can be used to bum coal in fuel beds. Mechanical stokers are designed to 
feed coal onto a grate within the furnace. The most common stoker type used in the utility 
industry is the spreader stoker (Figure 4-4). 6 In the spreader stoker, a flipping mechanism throws 
crushed coal into the furnace and onto a moving fuel bed (grate). Combustion occurs partly in 

o 

suspension and partly on the grate. 

Emission Control Techniques —Utility boilers are highly efficient and among the best 
controlled of all combustion sources. Existing emission regulations for total PM have 
necessitated controls on coal- and oil-fired utility sources. Emission controls are not required on 
natural gas boilers because, relative to coal and oil units, uncontrolled emissions are inherently 
low. 9 Baghouses. electrostatic precipitators (ESPs), wet scrubbers, and multicyclones have been 
used to control PM in the utility sector. As described in other source category sections, arsenic 
condenses on PM, which is easily controlled by PM control technologies. Particulate arsenic, 
specifically fine particulate, is controlled most effectively by baghouses or ESPs. Depending on 
their design, wet scrubbers are potentially effective in controlling particulate arsenic. 
Multicyclones are less effective at capturing fine particles of arsenic and, therefore, are a poor 
control system for arsenic emissions. 10 

A more recently applied S0 2 control technique for utility boilers is spray drying. In this 
process, the gas stream is cooled in the spray dryer, but it remains above the saturation 
temperature. A fabric filter or an ESP is located downstream of the spray dryer, thus controlling 


4-7 





Rue Gas 



Figure 4-3. Simplified Atmospheric Fluidized Bed Combustor Process Flow Diagram 
Source: Reference 6. 


4-8 


ERG POM 4124.ds4 

















































4-9 


Figure 4-4. Spreader Type Stoker-Fired Boiler 



































both particulate and vapor-phase arsenic compounds that condense before they reach the 
baghouse or ESP. 9,10 

Industrial/Commercial Sector 

Industrial boilers are widely used in manufacturing, processing, mining, and refining, 
primarily to generate process steam, electricity, or space heat at the facility. Only a limited 
amount of electricity is generated by the industrial sector; only 10 to 15 percent of industrial 
boiler coal consumption and 5 to 10 percent of industrial boiler natural gas and oil consumption 
are used for electricity generation. 11 Commercial boilers are used to provide space heating for 
commercial establishments, medical institutions, and educational institutions. 

Industrial boiler use is concentrated in four major industries: paper products, chemical 
products, food, and petroleum. The most commonly used fuels include natural gas, distillate and 
residual fuel oils, and coal in both crushed and pulverized form. 11,12,13 

Other fuels burned in industrial boilers are wood wastes, liquified petroleum gas, and 
kerosene. Wood waste is the only non-fossil fuel discussed here since few arsenic emissions are 
attributed to the combustion of liquified petroleum gas and kerosene. The burning of wood 
waste in boilers is confined to those industries where it is available as a by-product. It is burned 
both to obtain heat energy and to alleviate possible solid waste disposal problems. Generally, 
bark is the major type of wood waste burned in pulp mills. In the lumber, furniture, and plywood 
industries, either a mixture of wood and bark, or wood alone, is frequently burned. As of 1980, 
the most recent data identified, there were approximately 1,600 wood-fired boilers operating in 
the United States with a total capacity of over 100,000 million Btu/hr (30,000 MW thermal). 12 

Many of the same boiler types used in the utility sector are also used in the 
industrial/commercial sector; however, the average size boiler used in the industrial/ commercial 
sector is substantially smaller than the average size boiler used in the utility sector. In addition, a 
few boiler designs are used only by the industrial/commercial sector. For a general description of 


.4-10 


the major subassemblies and key thermal processes that occur in boilers, refer to Figures 4-1 to 
4-4 in the section on Utility Sector Process Description and the accompanying discussion. 

Stoker-Fired Boiler -Instead of firing coal in suspension (like the boilers described in the 
Utility Sector Process Description section), mechanical stokers can be used to bum coal in fuel 
beds. All mechanical stokers are designed to feed coal onto a grate within the furnace. The most 
common stoker types in the industrial/commercial sector are overfeed and underfeed stokers. In 
overfeed stokers, crushed coal is fed from an adjustable grate above onto a traveling or vibrating 
grate below. The crushed coal bums on the fuel bed as it progresses through the furnace. 
Conversely, in underfeed stokers, crushed coal is forced upward onto the fuel bed from below by 
mechanical rams or screw conveyors. 6,8 

Water-tube BoiIers --In water-tube boilers, water is heated as it flows through tubes 
surrounded by circulating hot gases. These boilers represent the majority (i.e., 57 percent) of 
industrial and commercial boiler capacity (70 percent of industrial boiler capacity). 11 Water-tube 
boilers are used in a variety of applications, from supplying large amounts of process steam to 
providing space heat for industrial and commercial facilities. These boilers have capacities 
ranging from 9.9 to 1,494 million Btu/hr (2.9 to 439.5 MW thermal), averaging about 
408 million Btu/hr (120 MW thermal). The most common types of water-tube boilers used in the 
industrial/commercial sector are wall-fired and stoker-fired boilers. Tangentially-fired and FBC 
boilers are less commonly used. 13 Refer to Figures 4-1 to 4-4 and the accompanying discussion 
in the section on Utility Sector Process Description for more detail on these boiler designs. 

Fire-tube and Cast Iron Boilers --Two other heat transfer methods used in the 
industrial/commercial sector are fire-tube and cast iron boilers. In fire-tube boilers, hot gas flows 
through tubes that are surrounded by circulating water. Fire-tube boilers are not available with 
capacities as large as water-tube boilers, but they are also used to produce process steam and 
space heat. Most fire-tube boilers have a capacity between 1.4 and 25 million Btu/hr (0.4 to 
7.3 MW thermal). Most installed fire-tube boilers bum oil or gas and are used primarily in 
commercial/institutional applications. 


4-11 








In cast iron boilers, the hot gas is also contained inside the tubes that are surrounded by 
the water being heated, but the units are constructed of cast iron instead of steel. Cast iron 
boilers are limited in size and are used only to supply space heat. Cast iron boilers range in size 
from less than 0.34 to 9.9 million Btu/hr. 13 

Wood Waste Boilers --The burning of wood waste in boilers is primarily confined to those 
industries where it is available as a by-product. Wood is burned both to obtain heat energy and 
to alleviate solid waste disposal problems. Wood waste may include large pieces such as slabs, 
logs, and bark strips as well as cuttings, shavings, pellets, and sawdust. 12 

Various boiler firing configurations are used to bum wood waste. One configuration that 
is common in smaller operations is the dutch oven or extension-type of furnace with a flat grate. 
This unit is used widely because it can bum very high-moisture fuels. Fuel is fed into the oven 
through apertures in a firebox and is fired in a cone-shaped pile on a flat grate. The burning is 
accomplished in two stages: (1) drying and gasification, and (2) combustion of gaseous products. 
The first stage takes place in a cell separated from the boiler section by a bridge wall. The 
combustion stage takes place in the main boiler section. 12 

In another type of boiler, the fuel-cell oven, fuel is dropped onto suspended fixed grates 
and is fired in a pile. The fuel cell uses combustion air preheating and positioning of secondary 
and tertiary air injection ports to improve boiler efficiency. 12 

In many large operations, more conventional boilers have been modified to bum wood 
waste. These modified units may include spreader stokers with traveling grates or vibrating grate 
stokers, as well as tangentially-fired or cyclone-fired boilers. Refer to Figures 4-1 to 4-4 and the 
accompanying discussion in the section on Utility Sector Process Description for more detail on 
these types of boilers. The spreader stoker, which can bum dry or wet wood, is the most widely 
used of these configurations. Fuel is dropped in front of an air jet that casts the fuel out over a 
moving grate. The burning is carried out in three stages: (1) drying, (2) distillation and burning 
of volatile matter, and (3) burning of fixed carbon. These operations often fire natural gas or oil 


4-12 




as auxiliary fuel. Firing an auxiliary fuel helps to maintain constant steam when the wood supply 
fluctuates or to provide more steam than can be generated from the wood supply alone. 12 

Sander dust is often burned in various boiler types at plywood, particle board, and 
furniture plants. Sander dust contains fine wood particles with a moisture content of less than 
20 percent by weight. The dust is fired in a flaming horizontal torch, usually with natural gas as 
an ignition aid or as a supplementary fuel. 12 

A recent development in wood-firing is the FBC (refer to Figures 4-1 to 4-4 and the 
accompanying discussion in Utility' Sector Process Description for more detail on this boiler 
t\pe). Because of the large thermal mass represented by the hot inert bed particles, FBCs can 
handle fuels with high moisture content (up to 70 percent, total basis). Fluidized bed combustors 
can also handle dirty fuels (up to 30 percent inert material). Wood material is pyrolyzed faster in 
a fluidized bed than on a grate due to its immediate contact with hot bed material. 12 

The composition of wood w-aste is expected to have an impact on arsenic emissions. The 
composition of wood waste depends largely on the industry from which it originates. Wood 
waste fuel can contain demolition debris like plastics, paint, creosote-treated wood, glues, 
synthetics, wire, cable, insulation, and so forth, which are potential sources of arsenic emissions. 
Pulping operations, for example, produce great quantities of bark along with sand and other 
noncombustibles. In addition, when fossil fuels are co-fired with wood waste, there is potential 
for additional arsenic emissions from the arsenic content of the fossil fuel. 14 

Waste Oil Combustion —Waste oil is another type of fuel that is burned primarily in small 
industrial/commercial boilers and space heaters. Space heaters (small combustion units generally 
less than 250,000 Btu/hr heat input) are common in automobile service stations and automotive 
repair shops where supplies of waste crankcase oil are available. 15 Waste oil includes used 
crankcase oils from automobiles and trucks, used industrial lubricating oils (such as metal 
working oils), and other used industrial oils (such as heat transfer fluids). Due to a breakdown of 
the physical properties of these oils and contamination by other materials, these oils are 
considered waste oils when they are discarded. 16 


4-13 




The Federal government has developed regulations for waste oil fuel under the Resource 
Conservation and Recovery Act (RCRA). The EPA has determined that as long as used oil is 
recycled (which includes burning it for energy recovery as well as re-refining it or other 
processes), it is not considered a hazardous waste under RCRA. 17 However, if a facility does 
bum used oil, that facility is subject to certain requirements under RCRA. 

EPA has established two categories of waste fuel: “on-specification” and 
“off-specification.” If the arsenic levels of the waste oil are 5 ppm or less, the waste oil is 
classified as “on-specification;” if the arsenic levels are greater than 5 ppm, the waste oil is 
classified as “off-specification”. 18 

If a facility is burning “on-specification” waste oil for energy recovery, that facility is 
only subject to certain reporting and recordkeeping requirements. 18 If a facility bums the waste 
oil in a space heater with heat input capacity less than 0.5 million Btu/hr and vents the exhaust to 
the ambient air, then that facility is not subject to any requirements. 19 

A facility burning “off-specification” waste oil for energy recovery must comply with 
additional requirements, including verification to EPA that the combusted oil was not mixed with 

90 

other hazardous wastes. 

Boilers designed to bum No. 6 (residual) fuel oils or one of the distillate fuel oils can be 
used to bum waste oil, with or without modifications for optimizing combustion. As an 
alternative to boiler modification, the properties of waste oil can be modified by blending it with 
fuel oil to the extent required to achieve a clean-burning fuel mixture. 

Coal Combustion -A very small amount of coal is used in the industrial/ commercial 
sector. Coal accounts for only 18 percent of the total firing capacity of fossil fuel used. The 
majority of coal combustion occurs in the utility sector. Refer to Figures 4-1 to 4-4 and the 

accompanying discussion in Utility Sector Process Description for more detail about these boiler 
types. 


4-14 




*9 

Emission Control Tcchniques -The amount of arsenic emissions from industrial/ 
commercial boilers depends primarily on two factors: (1) the type of fuel burned, and (2) the 
type of boiler used. The secondary influences on arsenic emissions are the operating conditions 
of the boiler and the APCD used. 

Emission controls for industrial boilers and their effectiveness in reducing arsenic 
emissions are very similar to those previously described for utility boilers. PM control in the 
industrial sector is achieved with baghouses, ESPs, wet scrubbers, and multicyclones. 

PM emissions from oil-fired industrial boilers generally are not controlled under existing 
regulations because emission rates are low. Some areas may limit S0 2 emissions from oil-firing 
by specifying the use of lower-sulfur-content oils. Natural gas-fired industrial boilers are also 
generally uncontrolled because of very low emissions. 9,10 

Wood-fired industrial boilers are typically controlled by multicyclones followed by 
venturi or impingement-type wet scrubbers for PM control. Some wood-fired boilers use ESPs 
for PM control. The effect of both control systems on arsenic emissions reduction is estimated to 
be similar to that obtained at coal-fired units using the same technology (i.e., potentially good 
PM and vaporous arsenic control with scrubbers, and effective PM arsenic control but no 
vaporous arsenic control with ESPs). 9,10 

4.1.2 Emission Factors for Utility, Industrial, and Commercial Fuel Combustion 

Extensive arsenic emissions data for utility, industrial, and commercial stationary external 
combustion sources are available in the literature. Because State and Federal air pollution 
regulations often require emissions testing for toxic air pollutants, a significant current database 
of arsenic emissions from these fuel combustion sources exists. 


4-15 



Emission factors for utility, industrial, and commercial stationary external combustion 
source categories, grouped according to the type of fuel burned, are presented in Tables 4-1 to 
4-12 and discussed under the following subheadings: 

• Wood waste combustion: 

-- Utility boilers (Table 4-1), 

-- Industrial boilers (Table 4-2), 

-- Commercial/institutional boilers (Table 4-3); 

• Coal combustion: 

-- Utility boilers (Table 4-4), 

-- Industrial boilers (Table 4-5), 

— Commercial/institutional boilers (Table 4-6); 

• Oil combustion: 

— Utility boilers (Table 4-7), 

— Industrial boilers (Table 4-8), 

— Commercial/institutional boilers (Table 4-9); 

• Waste oil combustion: 

- Industrial boilers (Table 4-10), 

- Commercial/institutional boilers (Table 4-11); and 

• Solid waste combustion: 

-- Utility boilers (Table 4-12). 


4-16 


Wood Waste Combustion 


Arsenic emission factors for wood waste combustion in utility, industrial, and 
commercial boilers are presented in Tables 4-1,4-2, and 4-3, respectively. A general 
uncontrolled emission factor in units of lb per ton of wood waste combusted on wet, as-fired 
basis of 50 percent moisture and 4,500 Btu/lb is given in each table. These emission factors are 
widely applicable to all utility, industrial, and commercial wood waste combustion SCC 
categories. 6 However, a wide range of boiler sizes, boiler and control device configurations, and 
fuel characteristics are reflected by these composite emission factors. For this reason, if 
site-specific information is available to characterize an individual combustion source more 
accurately, it is recommended that the reader locate the appropriate process-specific emission 
factor presented in the applicable table. 

The average emission factors for utility wood waste-fired boilers are presented in 

Table 4-1. ’ The emission factors represent a range of control configurations and wood waste 

12 

compositions. 


Average emission factors for industrial wood waste-fired boilers are presented in 
Table 4-2. 12 -22.23.24,25,26.27 ^ portion of emission factors included are based on a comprehensive 
toxic air emission testing program in California. The summarized results of the study were used 
to obtain the average arsenic emission factors. The emission factors represent a range of boiler 
designs and capacities, control configurations, and wood waste compositions. The study, 
conducted by the Timber Association of California (TAC), tested boiler types with capacities 
greater than 50,000 lb of steam per hour, including fuel cell, dutch oven, stoker, air injection, and 
fluidized bed combustors. The range of control devices represented in the sample set included 
multiple cyclones, ESPs, and wet scrubbers 22,23,25 


Wood waste-fired commercial/institutional boilers average emission factors are presented 
in Table 4-3. 12 These emission factors represent uncontrolled configurations and a range of 
wood waste compositions. 12 Many of the same emission factors can be found in the utility and 


4-17 



TABLE 4-1. ARSENIC EMISSION EACTORS POR WOOD WASTE-FIRED UTILITY BOILERS 


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4-18 












TABLE 4-2. ARSENIC EMISSION FACTORS FOR WOOD WASTE-FIRED INDUSTRIAL BOILERS 


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.4-19 














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4-20 













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4-21 









industrial wood waste-fired tables. This duplication is expected because the same types of 
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Coal Combustion 

Arsenic emission factors for coal-fired utility boilers are presented in Table 4-4. 8,28,29 
The table includes emission factors for anthracite, bituminous, subbituminous, and lignite 
coal-firing boilers. 

Arsenic emission factors for coal-fired industrial and commercial/institutional boilers are 
listed in Tables 4 _ 5 8 ’ 28 ’ 30 ’ 31 and 4-6, 8,28,32 respectively. Control configurations include 
uncontrolled and single cyclone controlled. 

Oil Combustion 

Emission factors for specific utility boiler and control device configurations are listed in 
Table 4-7. 33 - 34 - 35 Sources include residual and distillate oil-fired boilers. 

Arsenic emission factors for No. 6 oil-fired and distillate oil-fired industrial boilers are 
presented in Table 4-8. 33 The data used in factor development came from the testing of 
uncontrolled units. 

Arsenic emission factors for oil-fired commercial/institutional boilers are listed in 
Table 4-9. 33 

Arsenic emission factors for industrial and commercial/institutional waste oil combustion 
are shown in Tables 4-10 and 4-11, respectively. 15 Emission factors are available for small 
boilers and two basic types of uncontrolled space heaters: a vaporizing pot-type burner and an 
air atomizing burner. The use of both blended and unblended fuels are reflected in these 
factors. 15 


.4-22 


TABLE 4-4. ARSENIC EMISSION FACTORS FOR COAL-FIRED UTILITY BOILERS 


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O 

u 


o 

U 

CO 

O 

U 


O 

U 

co 

E 

O 

U 

04 

Urf 

O 

O 

u 

co 

k> 

o 

c/5 

vs 

3 

O 

CO 

O 

U 


vs 

3 

O 

o 

U 


vs 

3 

O 

CO 

E 

vs 

3 

O 

04 

4* 

O 

04 

£ 

vs 

3 

O 

_s 

•a 

04 

N 

‘ka 

E 

(A 

3 

O 

3 

•o 

04 

N 

‘k. 

B 

V) 

3 

O 

3 

3 

U. 

04 

3 

vs 

3 

O 

s 

$5 

u 

04 

•o 

vs 

3 

O 

C 

\J 

oo 

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04 

<a 

c 

£ 

5 

T3 

04 

_N 

'C 

E 

3 

■o 

04 

N 

Wt 

E 

,3 

IS 

04 

3 

'3 

s 

$5 

ka 

04 

•o 

i— 

04 

> 

3 

04 

> 

o 

E 

3 

04 

> 

o 

a 

_o 

"o 

1 

co 

04 

ka 

§ 

04 

> 

CO 

ka 

04 

> 

15 

.© 

04 

> 

o 

15 

X 5 

04 

> 

© 

15 

a© 

04 

15 

.© 

CO 

04 

ka 

o 

5 

2 

o 

m 

ffi 

1 

© 

m 

s 

U 

m 

Ck 

C/5 

5 

ka 

H 

o 

3 

C/5 

2 

o 

ffi 

3 

C/5 

£ 

o 

ffi 

3 

C/5 

u 

3 

C/1 

Ck 

C/5 


04 

4= 

E 

3 

z 

u 

u 

oo 


(N 

O 


© 

PS 


PS 

© 

8 


ro 

© 

i 

PS 


s 

PS 



PS 

m 


PS 

PS 

PS 

PS 

PS 

PS 

PS 

PS 

8 

8 

8 

8 





© 

© 

© 

© 






4-23 











TABLE 4-4. CONTINUED 


cj 

o 

c 

CJ 

ka 

A) 

t*—. 
0) 
a: 


00 


ON 

CN 


ON 

fS 


On 

<S 


On 

<N 


ON 

(S 


o 

re 

U_ oo 
a -S 
O re 
m Q£ 

t« 

E 

U3 


tU 


tu 


tU 


tu 


tu 


lU 


m 

■nT 


>. 

£> 

_>N 

a. 

3 

E 


\o 

© 

"Sb 

o 


CJ 

> 

C 

o 

o 

o 

H 


•o 

cj 

oo 

3 

E 

o 

u 

"re 

o 

o 

<4— 

O 

3 

ffl 

C 

o 


■ 8 . 

•a 

<u 


E 

CJ 

C 

re 


a 

u_ 

o 

jO 


■o 

cj 

C/J 

to 

V 

u- 

C- 

X 

OJ 

CJ 

ka 

re 

to 

ka 

O 

o 

<2 

C 

o 

So 

to 


tU 


<u 

GO 

§ "3 

* I 

k. 

O C 

U .2 

re — 
tu •'a 
e £ 
.2 x 

to ' 1 

.52 c 

E 

tU 


X 

m 

O 


"T 

o 

x 

fS 

■NT 


T 

ro 

O 

ro 

b 

O 


aaa 

■ 1 

X 

X 

X 

fS 

O 

0 

m 

—* 

— 

NO 

ri 

—• 

T 

b 

T 

O 

O 




X 

X 

X 

VO 

0 

00 

m 

—~ 

ro 

oi 


«o 


CJ 

re re 

tu B 
c m 
.2 c 

to o 
to .3 

E = 

tu 

CJ -C 
CO — 
re c 
1— .3 

OJ 

> 

< 


c u 
h .2 
c > 
c ^ 
U Q 


ro 

© 

X 

cn 

r~ 

CN 


ro 

o 

x 

Os 

m 


OJ 

c 


cj 

c 

o 

Z 


cj 

c 

o 

Z 


4> 

O 

4> 

C 

C 

C 

O 

O 

O 

Z 

Z 

Z 


<U 

CJ 

t— 

3 

0 


ka 


w 

OJ 

£ 



Q 






ka 



O 

in 

u 

c/3 

3 

0 > 

c 5 

Cj 

-X 

O 


"re 

O 



"re 

0 



<u 

0 

re 

e 


CJ 

re 

CJ 

0 . 


k. 

CJ 

c 

# o 

O 

r* 

Ua 

O 

55 

"re 

U 


re 

U 


re 

E 

3 

"re 

ka 

O 

55 

"re 

0 

c /5 



O 

•a 


O 

•0 


0 

fT 

O 


O 

55 

GO 

E 

tu 

E 

3 

S 

CO 

c 

"a> 

> 

w 

<U 

<*a 

U- 

OJ 

U 

OJ 

‘E 

cu 

_N 

Ua 

CJ 

> 

E 

0 

U 

4 J 

‘E 

o> 

'C 

OJ 

> 

E 

0 

U 

o> 

‘E 

« 

c 

0 

U 

CJ 

‘E 

CO 

.5 

"w 

> 

t" 

ka 

CJ 

U 

I) 

4-* 

'E 

ka 

CJ 

•0 

re 

CJ 


X. 

3 

CO 

re 

H 

> 

O 

CO 

J 

5 

0 

CD 

co 

J 

2 

0 

CQ 

00 

J 

CJ 

>v 

U 

co 

J 

re 

ha 

H 

> 

g 

CO 

J 

ka 

Q. 

CO 


a 

E 

3 

Z 

u 

u 

on 


>0 

rJ 



m 

O 

3 

8 

rj 

m 

m 

cn 

rn 

1 

m 

8 

8 

8 

8 

8 

8 

— 





1 

O 

1 

O 

O 

O 

O 

0 


4-24 










TABLE 4-5. ARSENIC EMISSION FACTORS EOR COAL EIRE!) INDUSTRIAL BOILERS 


4> 

u 

c 

4> 

ba 

<*-. 

0> 

OC 


00 

fS 


00 


00 


00 


00 


00 


o — 

cn cn 


oo 


oo 


oo 


u 
re 
U. M 

C-f 

O 03 

'So 0£ 

to 

E 

UJ 


tu 


UJ 


u 


u 


u 


u 


D D U 


w 


UJ 


u 

60 

0£ § 
u. “ 
C C 

O .2 

re — 

= 1 
.2 ^ 
to — 

3 


ix 


e 

o 


re’ 

© 

X 

o 

x- 

<s 


© 

x 

w-J 


T 

O 


s 

ri 


x 

m 

O 


T 

© 

x 

rs 

x; 

«n 


u 

re re 
U. 3 

3 © 


to c 
to .— 


o -3 
to — 


3 

C 

£ 

TT 


T 


O 

o 

*— 

■ i 

X 

X 

oc 

rr 

m 

00 


v© 


T 

O 

x 

vn 


o 

«o 

o 

T 

© 

T 

© 

X 

s 

X 

5 

X 

00 

cn 

X 

rr 

00 

r-" 

r- 

wi 

V© 


x 

»r> 


6) 

> 

< 


U “ 


1> 

U> 


4> 


4> 


4> 

4) 

4) 

4) 

4) 

4) 



3 

3 

3 

. c 

3 

3 

3 

3 

3 

3 

> 

c 

C 

O 

O 

o 

O 

O 

O 

O 

O 

O 


Z 

Z 

Z 

Z 

Z 

Z 

Z 

Z 

Z 

Z 

Z 


u 

u 

t— 

3 

O 

C/5 

3 

_C 

to 

CO 


1X1 


re 

o 

U 

v 

u 

re 


•o 

o 

t- 

4> 

> 

O 

o 

re 


~a 

o 

,<u 


3 

< 


60 

_s 

"w 
> 

2 2 
H C/5 




4> 

£ 

"re *3 

c3 8 
u u 

3 *0 

o « 

C* N 

•|"= E 
E o 

5 — = 

5 8 ca 



"re > 

O ^ 

§Q 

re 

O 

Ux 

Ux 

U 

s s 

oU 

3 8 
oU 

to 

3 

O 

•E ■o 

•E x) 

3 


5 £ m 


Is 

is 


2-c 


5 E- Cn 


3 p o 
oo a. CQ 


s > 

c^ © 


E 

o 

o 

as 



is 

E 

s 

© 

o 

cn 

O 

3 

«n 

© 

8 

cn 

CJ 

1 

C4 

cn 

<N 

3 

1 

i 

C4 

rsi 

8 


fN 

<N 

£>» 

(N 

(N 

(N 

(N 

z 

i 

8 

8 

8 

8 

8 

8 

8 

8 

8 

u 

i 

<N 

i 

r4 

<N 

fN 

fS 


<N 

rs 


i 

(N 

u 

o 

© 

O 

o 

O 

© 

o 

O 

O 

o 

O 

or: 

1 


i 

1 

1 

1 

1 

1 

1 

1 

i 


. 4-25 











TABLE 4-5. CONTINUED 


u 

u 

a 

9 J 

u. 

<U 

4> 

06 


o 

U. oc| 
C -s 

O 05 

‘35 06 

ITi 


UJ 


60 

S "a 

CQ 
o c 
o .2 

03 — 

C 1 
.2 x 

m 1 

.52 a 

E 

UJ 


u. 


O 


u 


C3 

ra 

U- 

3 

c 

Ud 

c 

c 



</3 


* 3 

‘ 

H 

. — 

UJ 




o 


CD 

—• 

cc 

c 

u- 


o 


> 


< 



00 


00 


c w 

Z. .U 
c > 

c w 
U Q 


SJ 

o 

On 

3 

o 

00 

e 

_o 

co 

oo 

E 

uj 


i! 

E 

3 

z 

u 

u 

oo 


UJ 


UJ 


'T 

o 

x 

<N 

''T 

wo 


T 

© 

x 

s 

fS 


ro 

© 

X 

ro 

O 


T 

© 

x 

<N 

tt 

wo 


o 

c 

o 


<u 

c 

o 

z 


re 


fO 

O 


o 

U 

0. 

U 

C/3 

OJ 

1/3 

3 

•X 

3 

O 

o 

O 

C 

OO 

c 

E 

Ua 

E 

3 

QJ 

-o 

3 

X 

0> 

X 

X 

u- 

X 

3 

Da 

3 

00 

C/D 

OO 


■o 

u 

& 

I— 

<D 
> 

o 

OJ 

03 

In 

o 

60 
_c 

13 & 

_ 2 O 
00 h" 00 


tt 

<N 

i 

Csl 


(N 

o 


wo 

(N 

i 

<N 


(N 

o 


PO 

Tf 


>* 

x 

Q. 

+■» 

3 

E 


60 


4> 

Q. 

■o 

OJ 


E 

4> 


a 

Cm 

o 

X) 


73 

<u 

m 

in 

4> 

Wn 

D. 

X 

<u 

D 

u. 

00 

kx 

O 

o 

<2 

c 

_o 

to 

oo 


UJ 

n 


4-26 











TABLE 4-6. ARSENIC EMISSION FACTORS FOR COAL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS 


4> 

u 

c 

4> 

,<u 

<u 

OC 


c 

O M 

5 2 .s 

CO O w 

•3 to to 
C u. Q£ 
UJ 


4) 

DO 

c 

TO " 

a: 


2 

02 

c 

o 


CJ 

TO _ 

UJ -p 
e -2 
.2 £ 
CO c 

2 

UJ 


c 

_o 

co 

1 = 

o 

4> TO 
DO UJ 
TO 
k~ 

4> 

> 

< 


02 

c 

o 


O 

u. .2 
C > 

c « 
U Q 


4) 

CJ 

U* 

3 

O 

on 

c 

.o 

co 

CO 

2 

LD 


00 

<N 


Hi 


c 

o 


T 

© 

*x 

© 

TO 

ri 


Q 

Z 


c 

o 


T 

© 

x 

5v 


00 00 


00 


00 


<N 

m 


oo oo 


oo 


UJ UJ 


uu 


UJ D 


UJ UJ 


Ui 


X 

m 

© 


© 

’x 

(N 

TO 

on 


"T 

© 

x 

fS 

TO 

on 

l 

T 

© 

x 

s 

ri 


4> 


2 

TO 

k— 

O 

DO 

e 

"53 

> 

TO 

ba 

U. I- 
r- u 

o 2 

CJ c/3 

Si ^ 

— 

CJ 0> 
CO u- 

Ua U. 

f §J 


4) 

£ 

E 

3 

UJ 

4> 

C 

o 

3 

>» 

U 

"to 

o 

U 

CO 

3 

O 

a 

2 

3 

£ 


4> 


& 




£ 


D 



k_> 

"to 


"to 


k> 

4> 

4> 

.X 

o 


o 


.X 

O 

U 


U 


o 

XX 

on 

to 


TO 


5n 

TO 

4» 


4) 


TO 

4) 

N 


N 


4> 

2 

'k. 


u. 


2 

k. 

4> 


4> 


k> 

4) 

> 


> 


4> 

TO 



£ 


> 

O 

C 

D 







c a 


ed 


Cd 

cz 

o 


o 


O 

c 

U 


U 


U 

u 

CO 


CO 


CO 

CO 

3 


3 


3 

3 

O 


O 


O 

O 

3 

2 

2 

o 

c 

2 

2 

o 

e 

2 

c 

I 

5 

o 

3 

o 

3 


£ 

02 

£ 

CD 

£ 

£ 


4) 

.X 

o 


^ -c 


4> 

•o 

TO 

4> 

i— 

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on 

"to 

o 

U 

CO 

3 

O 

c 


00 00 


00 


UJ Hi UJ 


m 

© © 
X X 

n m 

to; © 

on — 

i • 

T 'T 
© © 

X X 

to r) 
VO rr 

ri on 


T 

T 

T 

«n 

o 

T 

T 


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© 

© 

© 

© 

© 

w 

ax 

X* 


aH 

x-a 

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X 

X 

X 

! x 

! x 

X 

X 

on 

oc 

TO 

! vo 

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TO 

on 

— 

m 

00 

on 

m 

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on 

VO 

ri 

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4) 

4) 

4> 

4) 

4> 

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o 

4) 

4> 

4) 

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C 

C 

C 

C 

oo 2 

c 

C 

C 

C 

c 

o 

o 

o 

o 

c u 

o 

o 

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o 

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Z 

Z 

Z 

Z 

•- >> 
on 

Z 

Z 

Z 

Z 


4> 

C 

o 

Z 


4) 

C 

o 

Z 


4) 


TO 


"to 


CJ 

cd 

k> 

4> 

o 


O 


c 


U 


U 



O 

TO 


TO 


UJ 


4> 


4> 



u 

N 


N 


4> 

4) 

ba 


"C 


C 

TO 

4> 


4> 



TO 

> 


> 


u 

4> 

L- 

£ 


2 


u 

Cl 

on 

1 


i 


, 1 


H3 


cd 


cd 

TO 

o 


o 


o 

O 

U 


U 


U 

U 

CO 


CO 


CO 

CO 

3 


3 


3 

3 

O 

2 

O 

c 

2 

O 

c 

O 

c 


2 

TO 

k. 

O 

DO 

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4> 

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TO 


TO 

O u. 
CJ « 


CQ 



4> 

© 

r4 


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r* 

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n 

2 

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© 

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r» 

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r4 

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ri 

n 

n 

n 

r> 

z 

8 

8 

8 

8 

8 

8 

8 

8 

8 

u 

• 

i 

m 

m 

m 

r<n 

rn 

m 

m 

m 

u 

on 

© 

• 

© 

i 

© 

i 

© 

i 

© 

1 

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1 

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1 

© 

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1 


m to 

n n 

■ i 

n n 

8 8 

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r*n m 

© © 


on 

n 

■ 

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2L 

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2 

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X 


to 

4» 

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4> 

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4) 

4> 

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CO 

ba 

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u 

if? 

Ct— 

c 

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00 

CO 


ta 


4-27 


means data not available. 













TABLE 4-7. ARSENIC EMISSION FACTORS FOR OIL-FIRED UTILITY BOILERS 


1) 

O 

c 

<u 

c*—» 
4 J 

OS 


ec 
a -S 

O re 
c/5 OS 
•a •— 

E ° 

u a 

re 

UJ 


4J 

CO 

5 « 
2 2 
“ m 

o c 

o .2 
re —- 
UJ -a 
C £ 
.2 X) 

C/5 ~“ 

<= 


UJ 


u 

re « 

u. 2 

c co 
.2 c 

to c 
co 

'E — 
u3 E 

0> X 
CO ~ 

« c 

4 J 

> 

< 


CJ 

> 

o 

Q 


c 

o 

U 


o 

oo 

C 

_o 

c/5 

to 

E 

UJ 


o 

X 

E 

3 

2 

U 

U 

C/3 


ro 


Tt 

ro 


UJ 


T 

O 

X 

TT 


vi 

O 


VI 

o 

*x 

Ti¬ 

en 

SO 


NO 

o 

X 

o 

OS 


v 

o 

X 

© 

C4 


OJ 

c 

o 

2 


c 

c 

to •— 

O -I 

o o 

3 .!= 

E £ 

OS 


■o 

OJ 


re 


3^_ 

rE £> 

«3 • — 

4J o 
OS CQ 


m 

m 


UJ 


T 

© 

X 

'<3- 


v 

o 


o 

c 

o 

2 


•o 

OJ 


3 °k. 

TJ 5 

“ 

<D O 
OS 00 


*n 

m 


SO 

o 

X 

m 

r- 

so 


OJ 

c 

o 

2 


•o 

aj 


re _ 

3 a 

i- 

.a o 

CO 73 
4> O 

OS 00 


ro 

po 


U 


NO 

o 

x 

o 

rs 


aj 

3 

O 

2 


CO 

<u 

•o 

re 

u. 

o 


aj rs 

.*3 (S 
to "O 

5 g 


V) 


pn 

Tf 


>N 

X 

TL 

3 

E 


8 . 

■8 


0> 

w 

I 

J3 

1 

Cm 

O 

X 



FT . M • —■ IM 

.2 o O O 


E o o o 
UJ 2 2 2 

m jo o a 


is 

X 

_re 

"re 

> 

re 

o 

c 

re 

re 

•o 


4) 

E 



4-28 













TABLE 4-8. ARSENIC EMISSION FACTORS FOR OIL-FIRED INDUSTRIAL BOILERS 


o 

uu OC 

C -S 

% cS 

CO 


UJ 


u w 


0) 

oo 

* i 

o c 
t> .2 

C3 — 

u- •■= 
c E 
.2 x 

to — 

c 

E 

UJ 


T 

O 

x 

T 


© 


cj 

w ™ 

u. = 

c ca 

.2 c 

to O 
oo -JjS 

E -"E 
uj E 

4J X! 
OO —' 

2 .E 

y 

> 

< 


X 

o 

CN 


<U 

CJ 

’> 

CJ 

O 


o 

U 


cu 

c 

c 

Z 


cj 

c 

o 

Z 


cj 

CJ 

1— 

3 

C 

CO 

c 

_o 

to 

r— 

c 

UJ 


O 

(N 

•a 


O „ 


\o 

<v 

•a 

CO 

o 


CO 

3 

."2 

CJ 

a: 


CO 

y 

"O 

CO 

1— 

U 


o 

2 

c3 


£ 

E 

3 

z 

u 

u 

co 


© o 

Tj- 


(N <N 

o o 


cn 

cn 

CJ 

CJ 

c 

CJ 

U« 

t2 

« 

oz 


cj 

u 

t- 

3 

O 

CO 






4-29 









TABLE 4-9. ARSENIC EMISSION EACTORS FOR OIL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS 


U 

re 

U. 

c 

o 

*cc 

(A 


u 


04 

Of) 

g 

ex: 

t~ 

o 

o 

re 

U. 

c 

o 

Vi 

in 

E 

UJ 


u 

re 


LL 


C/5 

C/5 



04 

Of) 

re 


> 

< 




O 

U 


04 

u 

I— 

3 

c 

00 

c 

o 


o 


C/5 

C/5 


£ 

UJ 


re 

3 

.32 

u 

02 



o 

VC 

04 

•o 

re 

k. 

O 


ta 


vC 

b 

X 

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04 

c 

c 


Z 


o 

fN 

— T3 

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22 — 1 
re v 

— 04 

£ re 

5 o 


«/0 


m 

O 

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ro 

04 

o 

c 

04 

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04 

02 

44 

U 

u. 

3 

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U2 





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> 

re 

o 

c 

re 

CO 

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0/5 

1 

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£ 

f 

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3 



4-30 









TABLE 4-10. ARSENIC EMISSION FACTORS FOR WASTE OIL-FIRED INDUSTRIAL BOILERS 


O 
03 
U. M 
C 

c -5 

O CT3 
co CC 

CO 


u 


44 

o 

> 

44 

Q 


c 

o 

U 


44 

U 

b> 

3 

o 

c 

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UJ 


44 

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3 

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u 

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rs 

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x 

8 

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ri 

© 

x 

o 

r4 


44 

44 

C 

C 

o 

O 

Z 

Z 


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44 

N 

£ 

o 


44 44 

to £ 

CQ 


44 

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3 

CQ 

C£ 

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a 

r<3 


o 

44 

to 

cc 


m 


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m 

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44 

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h> 

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44 

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44 

44 

u. 

3 

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a 

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o 

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o 

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3 

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a 

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a 

V- 

O 

JD 


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44 

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CO 

44 

l. 

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X 

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44 

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O 

44 

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jy 

£> 

J2 

<3 

> 

03 

C 

c 

to 

TO 

•o 


£ 




4-31 









TABLE 4-11. ARSENIC EMISSION FACTORS FOR WASTE OIL-FIRED COMMERCIAL/INSTITUTIONAL BOILERS 


u 

CB 

tU M 

= -s 

o cB 
‘tn CC 

CO 


U 



m 


<D 

U 

> 

<v 

Q 


e 

o 

U 


<u 

CJ 

l_ 

3 

O 

m 

c 

_o 

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CO 

E 

tu 


o 

£> 


Z 

u 

u 

on 


Q O 


CM 

o 


X 

o 


— VO 


X 

O 

vn 

CN 


u 

a> 

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3 

r- 

C 

C 

c 

o 

Z 

Z 

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4> 




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CO 

b. 

■o 

<U 


3 

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JU 

CM 


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6 


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CD 

o 


N 

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1— 


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a 

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m 

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> 

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O 

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o 

u 

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aj 

OJ 

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F 

CO 

CB 

03 

k— 

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£ 

£ 

3 

m 

£ 




4J 

U 

c 

<u 


a 

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c 

u 

> 

c 

o 

u 

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© 

c 

u. 

3 

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CO 

CB 

Z 


a 

u- 

O 

X) 


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4J 

n 

w 

4> 

l_ 

a. 

x 

Q 

a> 

u. 

CB 

CO 

u. 

O 


X5 

CB 

‘cB 

> 

CB 

w 

o 

c 

CB 

CB 


CN 

o 

m 

nr 

u 

CB 


T3 

CO 

ro 

© 

CN 

8 

CN 

8 

cc 

c 

.o 

CO 

o 

CN 

§ 

r— 

1 

m 

i 

un 

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ii 

o 

CO 

o 

E 

O 

O 

o 

u 

c 


£ 

i 

1 

1 

3 

O 

UJ 

X! 

1 

| 


on 


4-32 










Solid Waste Combustion 


Arsenic emission factors for solid-waste fired utility boilers are presented in Table 4-12. 36 
The only control configuration represented is an ESP. Additional data regarding emissions from 
combustion of refuse derived fuel may be available from the Electric Power Research Institute 
(phone 415-855-2000) in Report No. TR104614. 

4.1.3 Source Locations 

Fuel economics and environmental regulations affect regional use patterns for 
combustion sources. Most of the U.S. utility coal-firing capability is east of the Mississippi 
River, with the significant remainder being in the Rocky Mountain region. Natural gas is used 
primarily in the South Central States and California. Oil is predominantly used in Florida and the 
Northeast. Information on precise utility plant locations can be obtained by contacting utility 
trade associations, such as the Electric Power Research Institute in Palo Alto, California, the 
Edison Electric Institute in Washington, D.C. (202-828-7400), or the U.S. Department of Energy 
(DOE) in Washington, D.C. Publications by EPA and DOE on the utility industry are useful in 
determining specific facility locations, sizes, and fuel use. 

Industrial and commercial coal combustion sources are located throughout the United 
States, but tend to be concentrated in areas of industry and larger population. Most of the 
coal-fired industrial boiler sources are located in the Midwest, Appalachian, and Southeast 
regions. Industrial wood-fired boilers tend to be located almost exclusively at pulp and paper, 
lumber products, and furniture industry facilities. These industries are concentrated in the 
Southeast, Gulf Coast, Appalachian, and Pacific Northwest regions. Trade associations such as 
the American Boiler Manufacturers Association in Arlington, Virginia (703-522-7350) and the 
Council of Industrial Boiler Owners in Fairfax Station, Virginia (703-250-9042) can provide 

on oo 

information on industrial boiler locations and trends. ’ 


4-33 


TABLE 4-12. ARSENIC EMISSION FACTOR FOR SOLID WASTE-FIRED UTILITY BOILERS 


Ui 


o 




o 


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UL. M 


c -S 

O TO 

P 

'S5 065 


C/3 


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.4-34 










4.2 Hazardous Waste Incineration 


Hazardous waste, as defined by RCRA in 40 CFR Part 261, 17 includes a wide variety of 
waste materials. Hazardous wastes are produced in the form of liquids (e.g., waste oils, 
halogenated and nonhalogenated solvents, other organic liquids, and pesticides/herbicides) and 
sludges and solids (e.g., halogenated and nonhalogenated sludges and solids, dye and paint 
sludges, resins, and latex). The arsenic content of hazardous waste varies widely, but arsenic 
could be emitted from the incineration of any of these types of hazardous waste. Based on a 
1986 study, total annual hazardous waste generation in the United States was approximately 
292 million tons. 39 Only a small fraction of the waste (less than 1 percent) was incinerated. In 
addition, the U.S. EPA has scheduled rulemaking to develop MACT standards for hazardous . 
waste combustors and cement kilns. The proposed standard should reduce arsenic emissions 
and is scheduled to be promulgated no later than 2000. 

Based on an EPA study conducted in 1983, the major types of hazardous waste streams 
incinerated were spent nonhalogenated solvents and corrosive and reactive wastes contaminated 
with organics. Together, these accounted for 44 percent of the waste incinerated. Other 
prominent wastes included hydrocyanic acid, acrylonitrile bottoms, and nonlisted ignitable 

40 

wastes. 


Industrial kilns, boilers, and furnaces are used to bum hazardous waste. They use the 
hazardous waste as fuel to produce commercial products such as cement, lime, iron, asphalt, or 
steam. In fact, the majority of hazardous waste generated in the United States is currently 
disposed of in cement kilns. Hazardous waste, which is an alternative to fossil fuels for energy 
and heat, is used at certain commercial facilities as a supplemental fuel. In the process of 
producing energy and heat, the hazardous wastes are subjected to high temperatures for a 
sufficient time to volatilize metals in the waste. 


4-35 


4.2.1 Process Description 


Hazardous waste incineration employs oxidation at high temperatures (usually 1,650°F or 

greater) to destroy the organic fraction of the waste and reduce volume. A diagram of the typical 

39 

process component options in a hazardous waste incineration facility is provided in Figure 4-5. 
The diagram shows the major subsystems that may be incorporated into a hazardous waste 
incineration system: waste preparation and feeding, combustion chamber(s), air pollution 
control, and residue/ash handling. 

Five types of hazardous waste incinerators are currently available and in operation: liquid 
injection, rotary kiln, fixed-hearth, fluidized-bed, and fume injection. 41 Additionally, a few other 
technologies have been used for incineration of hazardous*waste, including ocean incineration 
vessels and mobile incinerators. These latter processes are not in widespread use in the United 
States and are not discussed below. 

Liquid Injection Incinerators 

Liquid injection combustion chambers are used for pumpable liquid waste, including 
some low-viscosity sludges and slurries. Liquid injection units are usually simple, 
refractory-lined cylinders (either horizontally or vertically aligned) equipped with one or more 
waste burners. The typical capacity of liquid injection units is about 8 to 28 million Btu/hour. 
Figure 4-6 presents a schematic diagram of a typical liquid injection unit. 39,41 

Rotary Kiln Incinerators 

Rotary kiln incinerators are used for destruction of solid wastes, slurries, containerized 
waste, and liquids. Because of their versatility, these units are most frequently used by 
commercial off-site incineration facilities. Rotary kiln incinerators generally consist of two 
combustion chambers: a rotating kiln and an afterburner. The rotary kiln is a cylindrical 
refractory-lined shell mounted on a slight incline. The primary function of the kiln is to convert 
solid wastes to gases, which occurs through a series of volatilization, destructive distillation, and 


4-36 


Waste Preparation Combustion Air Pollution Control 



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4-37 


Figure 4-5. Typical Process Component Options in a Hazardous Waste Incineration Facility 







































4-38 


























partial combustion reactions. The typical capacity of these units is about 10 to 60 million 
Btu/hour. 

Figure 4-7 presents a schematic diagram of a typical rotary kiln unit. 39 An afterburner is 
connected directly to the discharge end of the kiln. The afterburner is used to ensure complete 
combustion of flue gases before their treatment for air pollutants. A tertiary combustion chamber 
may be added if needed. The afterburner itself may be horizontally or vertically aligned, and 
functions on much the same principles as the liquid injection unit described above. Both the 
afterburner and the kiln are usually equipped with an auxiliary fuel-firing system to control the 
operating temperature. 

Fixed-Hearth Incinerators 

Fixed-hearth incinerators (also called controlled-air, starved-air, or pyrolytic incinerators) 
are the third major technology used for hazardous waste incineration. 39 Figure 4-8 presents a 
schematic diagram of a typical fixed-hearth unit. 39,41 This type of incinerator may be used for 
the destruction of solid, sludge, and liquid wastes. Fixed-hearth units tend to be of smaller 
capacity (typically 5 million Btu/hour) than liquid injection or rotary kiln incinerators because of 
physical limitations in ram feeding and transporting large amounts of waste materials through the 
combustion chamber. 

Fixed-hearth units consist of a two-stage combustion process similar to that of rotary 
kilns. Waste is ram-fed into the primary chamber and burned at about 50 to 80 percent of 
stoichiometric air requirements. This starved-air condition causes most of the volatile fraction to 
be destroyed pyrolitically. The resultant smoke and pyrolysis products pass to the secondary 
chamber, where additional air and, in some cases, supplemental fuel, is injected to complete the 
combustion. 39 




4-39 





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4-40 


Figure 4-7. Typical Rotary Kiln/Afterburner Combustion Chamber 













































t 

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4-41 




























































Fluidized-Bed Incinerators 


Fluidized-bed incinerators (combustors), which are described in Section 4.4.1 of this 
report, have only recently been applied to hazardous waste incineration. FBCs used to dispose of 
hazardous waste are very similar to those used to incinerate sewage sludge except for their 
additional capability of handling liquid wastes. 

FBCs are suitable for disposing of combustible solids, liquids, and gaseous wastes. They 
are not suited for irregular or bulky wastes, tarry solids, or other wastes that leave residues in the 
bed 42 Fluidized-bed combustion chambers consist of a single refractory-lined combustion 
vessel partially filled with inert granular material (e.g., particles of sand, alumina, and sodium 
carbonate). 39 The typical capacity of this type of incinerator is 45 million Btu/hour. 

Fume Injection Incinerators 

Fume injection incinerators are used exclusively to destroy gaseous or fume wastes. The 
combustion chamber is comparable to that of a liquid-injection incinerator (Figure 4-6) in that it 
usually has a single chamber, is vertically or horizontally aligned, and uses nozzles to inject the 
waste into the chamber for combustion. Waste gases are injected by pressure or atomization 
through the burner nozzles. Wastes may be combusted solely by thermal or catalytic oxidation. 

Emission Control Techniques 

The types of incinerators used for hazardous waste combustion are similar to the 
incinerators used by the other combustion sources discussed earlier in this section. However, the 
components in the hazardous waste stream vary extensively. The hazardous waste stream may 
include a variety of liquid, solid, or sludge wastes considered hazardous by RCRA. The 
hazardous waste stream may also include wastes generated by a variety of sources (e.g., medical, 
municipal, and sewage sludge). 


4-42 


Controlling arsenic emissions is partly accomplished by monitoring the temperature of 
the combustion bed. Arsenic compounds vaporize at elevated temperatures. The higher the 
temperature, the larger the fraction of arsenic vaporized. As the temperature drops, a fraction of 
the arsenic condenses. Collection of arsenic condensed on PM occurs in the APCD. 43 

4.2.2 Emission Factors 

The composition of the hazardous waste varies tremendously in the hazardous waste 
incineration industry, such that the arsenic content of the waste stream also varies widely. The 
arsenic content of the waste being combusted dictates whether or not significant arsenic 
emissions occur. 

One emission factor for arsenic is reported in Table 4-13. 44 Additional emission factor 
data are not readily available. However, relevant test data may be available in Volume II of the 
draft Technical Support Document for the Hazardous Waste Combustion Rule (February 1996). 
Also, emission factor data may be available in databases developed by trade associations or other 
industry groups. 45 

4.2.3 Source Location 

Currently, 162 permitted or interim status incinerator facilities, having 190 units, are in 
operation in the U.S. Another 26 facilities are proposed (i.e., new facilities under construction or 
permitting). Of the above 162 facilities, 21 facilities are commercial facilities that bum about 
700,000 tons of hazardous waste annually. The remaining 141 are on-site or captive facilities 
and bum approximately 800,000 tons of waste annually. 


4-43 



TABLE 4-13. ARSENIC EMISSION FACTORS FOR HAZARDOUS WASTE INCINERATION 


o 

a -S 

s — 1 

O (Q 

"55 OC 

n 


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4-44 











43 Municipal Waste Combustion 


4.3.1 Process Description 

Municipal waste combustors (MWCs) bum garbage and other nonhazardous solid waste, 
commonly called municipal solid waste (MSW). Three main types of combustors are used to 
combust MSW: mass bum, refuse-derived fuel-fired (RDF), and modular. Each type is 
discussed below. 

Mass Bum Combustors 

In mass bum units, MSW is combusted without any preprocessing other than removal of 
items too large to go through the feed system. In a typical mass bum combustor, refuse is placed 
on a grate that moves through the combustor. Combustion air in excess of stoichiometric 
amounts is supplied both below (underfire air) and above (overfire air) the grate. Mass bum 
combustors are erected at the site (as opposed to being prefabricated) and range in size from 
50 to 1,000 tons/day of MSW throughput per unit. Mass bum combustors can be divided into 
mass bum/waterwall (MBAVW), mass bum/rotary waterwall (MB/RC), and mass bum/refractory 
wall (MB/REF) designs. 

The walls of a MBAVW combustor are constructed of metal tubes that contain 
pressurized water and recover radiant heat for production of steam and/or electricity. A typical 
MBAVW combustor is shown in Figure 4-9. With the MB/RC combustor, a rotary combustion 
chamber sits at a slight angle and rotates at about 10 revolutions per hour, causing the waste to 
advance and tumble as it bums. The combustion cylinder consists of alternating water tubes and 
perforated steel plates. Figure 4-10 illustrates a simplified process flow diagram for a MB/RC. 
MB/REF designs are older and typically do not include any heat recovery. One type of MB/REF 
combustor is shown in Figure 4-11. 46 


4-45 


TT 



4-46 


Figure 4-9. Typical Mass Bum Waterwall Combustor 




























































Superheater 



4-47 


Figure 4-10. Simplified Process Flow Diagram, Gas Cycle for a Mass Bum/Rotary Waterwall Combustor 

































































































NO 

•*r 

o 

o 

c 

<u 

V 

CC 


o 

o 


o 

CO 


4-48 


Figure 4-11. Mass Burn Refractory-Wall Combustor with Grate/Rotary Kiln 
























































































































•i' 

RDF-Fired Combustors 

RDF-fired combustors bum processed waste that varies from shredded waste to finely 
divided fuel suitable for co-firing with pulverized coal. Combustor sizes range from 320 to 

i 

1,400 tons/day. There are three major types of RDF-fired combustors: dedicated RDF 
combustors, which are designed to bum RDF as a primary fuel; coal/RDF co-fired combustors; 
and fluidized-bed combustors (FBCs) where waste is combusted on a turbulent bed of limestone, 
sand, silica or aluminum. 

A typical RDF-fired combustor is shown in Figure 4-12. 46 Waste processing usually 
consists of removing noncombustibles and shredding, which generally raises the heating value 
and provides a more uniform fuel. The type of RDF used depends on the boiler design. Most 

9 . 

boilers designed to bum RDF use spreader stokers and fire fluff RDF in a semi-suspension mode 

Modular Combustors 

Modular combustors are similar to mass bum combustors in that they bum waste that has 
not been pre-processed, but they are typically shop-fabricated and generally range in size from 
5 to 140 tons/day of MSW throughput. One of the most common types of modular combustors is 
the starved-air or controlled-air type, which incorporates two combustion chambers. A process 
diagram of a typical modular starved-air (MOD/SA) combustor is presented in Figure 4-13. 46 
Air is supplied to the primary chamber at sub-stoichiometric levels. The incomplete combustion 
products (CO and organic compounds) pass into the secondary combustion chamber, where 
additional air is added and combustion is completed. Another design is the modular excess air 
(MOD/EA) combustor, which consists of two chambers, similar to MOD/SA units, but is 
functionally like the mass bum unit in that it uses excess air in the primary chamber. 

Emission Control Techniques 

Arsenic is present in a variety of MSW streams, including paper, inks, batteries, and 
metal cans. Because of the wide variability in MSW composition, arsenic concentrations are 


4-49 


Superfieater 


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TT 

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oc 


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C/D 


4-50 


Figure 4-12. Typical RDF-Fired Spreader Stoker Boiler 


















































































































































ffi 


jp’sicTwocfofcB 


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4-51 


Figure 4-13. Typical Modular Starved-Air Combustor with Transfer Rams 




































highly variable and are independent of combustor type. Because the vapor pressure of arsenic is 
such that condensation occurs onto particulates in the flue gas, arsenic can be effectively 
removed by a PM control device. 46 

Because arsenic is usually emitted from MWCs in particulate form, the control of arsenic 
is most frequently accomplished through the use of an ESP or fabric filter (FF), which are 
common PM control techniques. Although other PM control technologies (e.g., cyclones, 
electrified gravel beds, and venturi scrubbers) are available, they are not as effective as the ESP 
or FF at removing PM and so are seldom used on existing systems. 46 Well-designed ESPs and 
FFs operated at 450°F or less remove over 97 percent of arsenic and other metals. 47 

The most common types of ESPs are plate-and-wire units, in which the discharge 
electrode is a bottom-weighted or rigid wire, and flat plate units, which use flat plates rather than 
wires as the discharge electrode. As a general rule, the greater the amount of collection plate 
area, the greater the PM collection efficiency. After the charged particles are collected on the 
grounded plates, the resulting dust layer is removed from the plates by rapping or washing, and 
collected in a hopper. As the dust layer is removed, some of the collected PM becomes 
re-entrained in the flue gas. To ensure good PM collection efficiency during plate cleaning and 
electrical upsets, ESPs have several fields located in series along the direction of flue gas flow 
that can be energized and cleaned independently. Particles re-entrained when the dust layer is 
removed from one field can be recollected in a downstream field. Because of this phenomenon, 
increasing the number of fields generally improves PM removal efficiency. 46 

4.3.2 Emission Factors 

Available arsenic emission factor data for several types of MWCs are provided in 
Table 4-14 46 The column labeled “Emission Source’’ identifies the main characteristics of each 
incinerator type. For some types of incinerators, a range of factors is provided that represents 
different sample test runs of the same source. Generally, there is a wide range in the emission 
factors associated with MWCs. This range is attributable to the variability of waste compositions 
and to the operating practices and effectiveness of control devices. 48 Waste composition can 


4-52 


TABLE 4-14. ARSENIC EMISSION FACTORS FOR MUNICIPAL WASTE COMBUSTION SOURCES 


u 
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4-55 


Fabric Filter. 













differ from one MWC unit to another, especially where the permit specifications for the accepted 
waste are different. Because of this variability, the factors shown in Table 4-14 must be used 
cautiously and may not be representative of other MWCs. Also, emission factor data may be 
available in databases developed by trade associations or other industry groups. 45 

4.3.3 Source Location 

In 1997, there were 120 MWC plants operating in the United States with a total capacity 
of approximately 111,000 tons/day of MSW. Table 4-15 lists the geographical distribution of 
MWC units and statewide capacities. 49 

4.4 Sewage Sludge Incinerators 

4.4.1 Process Description 

The first step in the process of sewage sludge incineration is dewatering the sludge. 

Sludge is generally dewatered until it is about 15 to 30 percent solids, at which point it will bum 
without supplemental fuel. After dewatering, the sludge is sent to the incinerator for combustion. 
The two main types of sewage sludge incinerators (SSIs) currently in use are the multiple-hearth 
furnace (MHF) and the fluidized-bed combustor (FBC). Over 80 percent of the identified 
operating SSIs are MHFs and about 15 percent are FBCs. The remaining SSIs co-fire MSW with 
sludge. 50 

Multiple-Hearth Furnaces 

A cross-sectional diagram of a typical MHF is shown in Figure 4-14. 50 The basic MHF is 
a vertically oriented cylinder. The outer shell is constructed of steel and lined with refractory 
material and surrounds a series of horizontal refractory hearths. A hollow cast iron rotating shaft 
runs through the center of the hearths. Cooling air is introduced into the shaft, which extends 
above the hearths. Attached to the central shaft are the rabble arms, which extend above the 


4-56 


TABLE 4-15. SUMMARY OF GEOGRAPHICAL DISTRIBUTION OF MWC 

FACILITIES (1997). 


State 

Number of 
MWC Facilities 

State MWC Capacity 
in tons/day 

Percentage of Total 
U.S. MWC Capacity 

Alabama 

1 

690 

<1 

Alaska 

2 

90 

<1 

Arkansas 

1 

40 

<1 

California 

3 

2,540 

2 

Connecticut 

6 

6,535 

6 

Florida 

13 

18,126 

16 

Georgia 

1 

500 

<1 

Hawaii 

1 

1,850 

2 

Illinois 

1 

1,200 

1 

Indiana 

1 

2,361 

2 

Iowa 

3 

282 

<1 

Maine 

4 

2,400 

2 

Maryland 

3 

4,410 

4 

Massachusetts 

8 

12,523 

11 

Michigan 

4 

2,525 

5 

Minnesota 

15 

7,930 

7 

Mississippi 

1 

150 

<1 

New Hampshire 

2 

700 

<1 

New Jersey 

6 

6,099 

6 

New- York 

10 

11,173 

10 

North Carolina 

1 

850 

<1 

Oklahoma 

1 

1,125 

1 

Oregon 

1 

550 

<1 

Pennsylvania 

9 

9,492 

9 

Tennessee 

2 

2,510 

2 

Texas 

5 

269 

<1 


4-57 









TABLE 4-15. CONTINUED 


State 

Number of 
MWC Facilities 

State MWC Capacity 
in tons/day 

Percentage of Total 
U.S. MWC Capacity 

Utah 

1 

420' ' 

<1 

Virginia 

6 

8,135 

8 

Washington 

5 

1,620 

1 

Wisconsin 

3 

520 

<1 

TOTAL 

120 

110,855 

100 


Source: Reference 49. 


4-58 







Furnace Exhaust 
to Afterburner 


4 
4 
4 

ft* Floating Damper 

▲ 



Figure 4-14. Typical Multiple-Hearth Furnace 

Source: Reference 50. 


4-59 


ERG POM 4331 cdr 



















































































































hearths. Each rabble arm is equipped with a number of teeth approximately 6 inches in length 
and spaced about 10 inches apart. The teeth are shaped to rake the sludge in a spiral motion, 
alternating in direction from the outside in to the inside out between hearths. Burners, which 
provide auxiliary heat, are located in the sidewalls of the hearths.. 

In most MHFs, partially dewatered sludge is fed onto the perimeter of the top hearth. The 
rabble arms move the sludge through the incinerator by raking the sludge toward the center shaft, 
where it drops through holes located at the center of the hearth. In the next hearth, the sludge is 
raked in the opposite direction. This process is repeated in all of the subsequent hearths. The 
effect of the rabble motion is to break up solid material to allow better surface contact with heat 
and oxygen. A sludge depth of about 1 inch is maintained in each hearth at the design sludge 
flow rate. 

Under normal operating conditions, 50 to 100 percent excess air must be added to an 
MHF to ensure complete combustion of the sludge. Besides enhancing contact between the fuel 
and the oxygen in the furnace, these relatively high rates of excess air are necessary to 
compensate for normal variations in both the organic characteristics of the sludge feed and the 
rate at which it enters the incinerator. When an inadequate amount of excess air is available, 
only partial oxidation of the carbon will occur, with a resultant increase in emissions of CO, soot, 
and hydrocarbons. Too much excess air, on the other hand, can cause increased entrainment of 
particulate and unnecessarily high auxiliary fuel consumption. 50 

Fluidized-Bed Combustors 

Figure 4-15 shows the cross-section diagram of an FBC. 50 FBCs consist of a vertically 
oriented outer shell constructed of steel and lined with refractory material. Tuyeres (nozzles 
designed to deliver blasts of air) are located at the base of the furnace within a refractory-lined 
grid. A bed of sand approximately 2.5 feet thick rests upon the grid. Two general configurations 
can be distinguished based on how the fluidizing air is injected into the furnace. In the hot 


4-60 


Exhaust and Ash 



Figure 4-15. Fluidized-Bed Combustor 


Source: Reference 50. 


4-61 



































































































































windbox design, the combustion air is first preheated by passing it through a heat exchanger, 
where heat is recovered from the hot flue gases. Alternatively, ambient air can be injected 
directly into the furnace from a cold windbox. 

Partially dewatered sludge is fed into the lower portion of the furnace. Air injected 
through the tuyeres at a pressure of 3 to 5 pounds per square inch gauge simultaneously fluidizes 
the bed of hot sand and the incoming sludge. Temperatures of 1,400 to 1,700°F are maintained 
in the bed. As the sludge bums, fine ash particles are carried out of the top of the furnace. Some 
sand is also removed in the air stream and must be replaced at regular intervals. 

Combustion of the sludge occurs in two zones. Within the sand bed itself (the first zone), 
evaporation of the water and pyrolysis of the organic materials occur nearly simultaneously as the 
temperature of the sludge is rapidly raised. In the freeboard area (the second zone), the 
remaining free carbon and combustible gases are burned. The second zone functions essentially 
as an afterburner. 

Fluidization achieves nearly ideal mixing between the sludge and the combustion air; the 
turbulence facilitates the transfer of heat from the hot sand to the sludge. An FBC improves the 
burning atmosphere, such that a limited amount of excess air is required for complete 
combustion of the sludge. Typically, FBCs can achieve complete combustion with 20 to 
50 percent excess air, about half the excess air required by MHFs. As a consequence, FBCs 
generally have lower fuel requirements compared to MHFs. 50 

Emission Control Techniques 

Certain conditions that affect the emission rates of arsenic in SSIs include: 

• Sludge metal content; 

• Operating bed temperature; 

• Flow patterns leading to solids drop-out ahead of APCD; and 


4-62 


• APCD control efficiency as a function of particle size. 

Clearly, the quantity of arsenic in the feed sludge is the basic scalar of emissions. Arsenic 
in sludge arises from several sources, including industrial discharges (especially plating wastes), 
corrosion of outtake plumbing materials, street runoff, and numerous lesser domestic and 
industrial activities. The arsenic content varies from day to day, reflecting a diversity of waste 
types. 


The temperature of the combustion environment influences the behavior of arsenic 
emissions because of the following sequence of events during incineration: 

1. At elevated temperatures, many heavy metal compounds (including arsenic) 
vaporize. The higher the temperature, the larger the fraction of metals that is 
vaporized. 

2. As temperatures drop, a fraction of the metals condenses. Condensation takes 
place in proportion to available surface area. 

3. Collection of the metals condensed on the PM occurs while passing through the 
APCD system. 43 

Arsenic emissions may be reduced by using PM control devices and reducing incinerator 
and APCD temperatures. The types of existing SSI PM controls include low-pressure-drop spray 
towers, wet cyclones, high-pressure-drop venturi scrubbers, and venturi/impingement tray 
scrubber combinations. A few ESPs and baghouses are employed, primarily where sludge is 
co-fired with MSW. The most widely used PM control device applied to an MHF is the 
impingement tray scrubber. Older units use the tray scrubber alone; combination 
venturi/impingement tray scrubbers are widely applied to newer MHFs and some FBCs. 50 

4.4.2 Emission Factors 

Table 4-16 presents arsenic emission factors for SSIs. 50,51,52 The factors presented cover 
the two main incinerator types: MHFs and FBCs. Again, as the emission factor tables for the 
other types of incinerators (previously discussed) show, PM type control technologies offer the 


4-63 


TABLE 4-16. ARSENIC EMISSION EACTORS EOR SEWAGE SLUDGE INCINERATOR SOURCES 


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4-65 











greatest efficiency for reducing arsenic emissions. Specifically, the FF and the venturi scrubber 
with impingement-type wet scrubber are the most effective control devices according to this set 
of data. Collection efficiencies for the control devices shown in Table 4-16 range from 80 to 
greater than 99 percent. 

4.4.3 Source Location 

There are approximately 200 sewage sludge incineration plants operating in the United 
States. 53 Most SSIs are located in the eastern United States, although there are a significant 
number on the West Coast. New York has the largest number of facilities with 33; Pennsylvania 
and Michigan have the next largest number with 21 and 19 sites, respectively. 54 

4.5 Medical Waste Incineration 

Medical waste incinerators (MWIs) bum both infectious (“red bag” and pathological) 
medical wastes and non-infectious general hospital wastes. The primary purposes of MWIs are 
to (1) render the waste innocuous, (2) reduce the volume and mass of the waste, and (3) provide 
waste-to-energy conversion. 

4.5.1 Process Description 

Three main types of incinerators are used as MWIs: controlled-air or starved-air, 
excess-air, and rotary kiln. The majority (>95 percent) of incinerators are controlled-air units. A 
small percentage (<2 percent) are excess-air, and less than 1 percent were identified as rotary 
kiln. The rotary kiln units tend to be larger and typically are equipped with air pollution control 
devices. 55 Based on EPA’s 1995 inventory, twenty-six percent of all MWI’s are equipped with 
air pollution control devices. 56 


4-66 


Controlled-Air Incinerators 


Controlled-air incineration is the most widely used MWI technology, and now dominates 
the market for new systems at hospitals and similar medical facilities. This technology is also 
known as two-stage incineration or modular combustion. Figure 4-16 presents a schematic 
diagram of a typical controlled-air unit. 55 

Combustion of waste in controlled-air incinerators occurs in two stages. In the first stage, 
waste is fed into the primary, or lower, combustion chamber, which is operated with less than the 
stoichiometric amount of air required for combustion. Combustion air enters the primary 
chamber from beneath the incinerator hearth (below the burning bed of waste). This air is called 
primary or underfire air. In the primary (starved-air) chamber, the low air-to-fuel ratio dries and 
facilitates volatilization of the waste and most of the residual carbon in the ash bums. At these 
conditions, combustion gas temperatures are relatively low (1,400 to 1,800°F). 55 

In the second stage, excess air is added to the volatile gases formed in the primary 
chamber to complete combustion. Secondary chamber temperatures are higher than primary 
chamber temperatures-typically 1,800 to 2,000°F. Depending upon the heating value and 
moisture content of the waste, additional heat may be needed. Additional heat can be provided 
by auxiliary burners located at the entrance to the secondary (upper) chamber to maintain desired 
temperatures. 55 

Waste feed capacities for controlled-air incinerators range from about 75 to 6,500 lb/hr 
(at an assumed fuel heating value of 8,500 Btu/lb). Waste feed and ash removal can be manual 
or automatic, depending on the unit size and options purchased. Throughput capacities for 
lower-heating-value wastes may be higher because feed capacities are limited by primary 
chamber heat release rates. Heat release rates for controlled-air incinerators typically range from 
about 15,000 to 25,000 Btu/hr-ft 3 . 55 


4-67 



I 



Figure 4-16. Controlled-Air Incinerator 


Source: Reference 55. 


4-68 


































































































Excess-Air Incinerators 


Excess-air incinerators are typically small, modular units. They are also referred to as 
batch incinerators, multiple-chamber incinerators, or “retort” incinerators. Excess-air 
incinerators are typically a compact cube with a series of internal chambers and baffles. 

Although they can be operated continuously, they are usually operated in batch mode. 55 

Figure 4-17 presents a schematic for an excess-air unit. 55 Typically, waste is manually 
fed into the combustion chamber. The charging door is then closed, and an afterburner is ignited 
to bring the secondary chamber to a target temperature (typically 1,600 to 1,800°F). When the 
target temperature is reached, the primary chamber burner ignites. The waste is dried, ignited, 
and combusted by heat provided by the primary chamber burner, as well as by radiant heat from 
the chamber walls. Moisture and volatile components in the waste are vaporized and pass (along 
with combustion gases) out of the primary chamber and through a flame port that connects the 
primary chamber to the secondary or mixing chamber. Secondary air is added through the flame 
port and is mixed with the volatile components in the secondary chamber. Burners are also 
installed in the secondary chamber to maintain adequate temperatures for combustion of volatile 
gases. Gases exiting the secondary chamber are directed to the incinerator stack or to an air 
pollution control device. After the chamber cools, ash is manually removed from the primary 
chamber floor and a new charge of waste can be added. 55 

Incinerators designed to bum general hospital waste operate at excess air levels of up to 
300 percent. If only pathological wastes are combusted, excess air levels near 100 percent are 
more common. The lower excess air helps maintain higher chamber temperature when burning 
high-moisture waste. Waste feed capacities for excess-air incinerators are usually 500 lb/hr or 

less. 55 


Rotary Kiln Incinerators 

Rotary kiln incinerators are also designed with a primary chamber, where the waste is 
heated and volatilized, and a secondary chamber, where combustion of the volatile fraction is 


4-69 



Side View 



Figure 4-17. Excess-Air Incinerator 


Source: Reference 55. 


4-70 


ERG Lead 513.cdr 
















































completed. The primary chamber consists of a slightly inclined, rotating kiln in which waste 
materials migrate from the feed end to the ash discharge end. The waste throughput rate is 
controlled by adjusting the rate of kiln rotation and the angle of inclination. Combustion air 
enters the primary chamber through a port. An auxiliary burner generally is used to start 
combustion and maintain desired combustion temperatures. 

Figure 4-18 presents a schematic diagram of a typical rotary kiln incinerator. Volatiles 
and combustion gases pass from the primary chamber to the secondary chamber. The secondary 
chamber operates at excess air. Combustion of the volatiles is completed in the secondary 
chamber. Because of the turbulent motion of the waste in the primary chamber, solids burnout 
rates and particulate entrainment in the flue gas are higher for rotary kiln incinerators than for 
other incinerator designs. As a result, rotary kiln incinerators generally have add-on gas-cleaning 
devices. 55 

Emission Control Techniques 

A majority of arsenic and other metal emissions are in the form of PM, and a minority is 
in vapor form. Particulate emissions of arsenic from the incineration of medical wastes are 
determined by three major factors: 

1. Suspension of noncombuStible inorganic materials containing arsenic; 

2. Incomplete combustion of combustible arsenic materials; and 

3. Condensation of arsenic-based vaporous materials (these materials are mostly 
inorganic matter). 

Emissions of noncombustible materials result from the suspension or entrainment of ash 
by the combustion air added to the primary chamber of an incinerator. The more air that is 
added, the more likely that noncombustibles become entrained. Particulate emissions from 
incomplete combustion of combustible materials result from improper combustion control of the 
incinerator. Condensation of vaporous materials results from noncombustible substances that 


4-71 


Exhaust Gas to Stack or 
Air Pollution Control Device" 



4-72 


Source: Reference 55. 

























volatilize at primary combustion chamber temperatures with subsequent cooling in the flue gas. 
These materials usually condense on the surface of other fine particles. 57 

Typically, two strategies are used to minimize metals emissions: (1) combustion control 
in the primary chamber so as to reduce vaporization or entrainment of metals, and (2) capture of 
metals by use of an APCD. Both of these strategies are discussed below. The key APCD 
parameters used are specific to the device that is used. 

Combustion Control -Most MWIs are simple single-chamber units with an afterburner 
located in the stack. The ability of batch incinerators to control arsenic emissions is limited 
because only the temperature in the stack is usually monitored. 

Most new incinerators are starved-air units. The primary chamber is designed to operate 
at low' temperatures and low gas flow rates. This minimizes the amount of materials entrained or 
vaporized. 

To ensure that arsenic emissions are minimized, operators must maintain the primary 
chamber at the temperatures and gas flow rates for which it was designed. Usually the only 
parameter that system operators can directly control is feed rate. High feed rates can lead to high 
temperatures and high gas velocities. Thus, many operators carefully control the feed rate. The 
feed rate is reduced when primary temperatures increase. Keeping the temperature low enables 
the arsenic to condense on different sizes of particles, which are then easily trapped by PM 
control devices. 

APCD Control --When arsenic reaches the APCD, it is present in one of three forms. 
Non-volatile arsenic is present on large entrained particles. Arsenic that has vaporized and 
recondensed is usually enriched on fly-ash particles with diameters less than 1 micron. Other 
arsenic may be present as vapor. 57 The majority of arsenic emissions are in the first two forms 
and are controlled by PM control devices. Generally, particulate control is a surrogate for arsenic 
control in an incinerator/air pollution control system. 4 


4-73 




4.5.2 Emission Factors 


The available arsenic emission factors for MWIs are presented in Table 4-17. 55,58,59 
Also, emission factor data may be available in databases developed by trade associations or other 
industry groups. 45 As with the other types of incinerators, waste composition is a critical factor 
in the amount of arsenic emitted. 

The arsenic emission factors were developed from tests at facilities burning red bag 
waste, pathological waste, and/or general hospital waste. Red bag waste is defined as any waste 
generated in the diagnosis or immunization of human beings or animals; pathological waste is 
defined as any human and animal remains, tissues, and cultures; and general hospital waste was 
defined as a mixture of red bag waste and municipal waste generated by the hospital. 

As with other combustion sources, the presented emission factors are highly dependent 
upon the composition of the waste. For example, the difference in the emission factors presented 
in Table 4-17 for both a high efficiency and medium efficiency wet scrubber with a fabric filter 
applied to an MWI is expected to be more a function of the arsenic content of the waste burned 
rather than scrubber efficiency. 

4.5.3 Source Location 

There are an estimated 2,400 MWIs in the United States, located at such facilities as 
hospitals, health care facilities, and commercial waste disposal companies to dispose of hospital 
waste and medical/infectious waste. Most MWIs are located at hospitals. 4 Of the approximately 
7,000 hospitals in the United States, fewer than half have MWIs. 60 


4-74 


TABLE 4-17. ARSENIC EMISSION FACTORS FOR MEDICAL WASTE INCINERATION SOURCES 


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4-76 











4.6 Crematories 


4.6.1 Process Description 

Crematory incinerators used for human cremation at funeral homes, mortuaries, 
cemetaries, and crematories are normally of an excess air design. They utilize secondary 
chamber (afterburner) and primary chamber (ignition) burners fueled by liquified petroleum (LP) 
gas or natural gas. Burner capacities are generally between 750,000 and 1,500,000 BTUs per 
hour per burner. Late model units have burner modulation capability to regulate chamber 
temperatures and conserve fuel. Incineration rates range from 100 to 250 pounds of remains per 
hour. 

Preheating and a minimum secondary chamber temperature, typically ranging from 
1,400°F to 1,800°F, may be requirements. Although not suitable for this batch load type, of 
incinerator, the same requirements are occasionally applied to the primary chamber. 

The human remains and cremation container, generally made of cardboard or wood, are 
loaded onto the primary chamber hearth and the primary burner is ignited to begin the cremation 
process. The remains may be raked at the midpoint of the cremation to uncover unbumed 
material and speed the process. The average cremation takes from 1-1/2 to 3 hours, after which 
the incinerator is allowed to cool for at least 30 minutes so that the remains can be swept from 
the hearth . 61 

4.6.2 Emission Factors 

Evaluation tests on two propane-fired crematories at a cemetery in California were 
conducted through a cooperative effort with the Sacramento Metropolitan Air Quality 
Management District to determine HAP emissions from a crematory. 62 The units were calibrated 
to operate at a maximum of 1.45 million Btu per hour. Emissions testing was performed over a 


4-77 


two-week period. Thirty-six bodies were cremated during the test period. The body, cardboard, 
and wood process rates for each test per crematory were reported. 

Sampling, recovery, and analysis for arsenic were performed in accordance with CARB 
Method 436. An emission factor developed from these data is presented in Table 4-18. 

4.6.3 Source Locations 

In 1991, there were about 400,000 cremations in more than 1,000 crematories located 
throughout the United States. Table 4-19 lists the number of crematories located in each State 
and the estimated number of cremations performed in each State. J 

4.7 Stationary Internal Combustion Sources 

4.7.1 Emissions 

Air emissions from the flue gas stack are the only emissions from electricity generation, 
industrial turbines, and reciprocating engines. Internal combustion engines or turbines firing 
distillate or residual oil may emit trace metals carried over from the metals content of the fuel. 

If the fuel analysis is known, the metals content of the fuel should be used for flue gas 
emission factors, assuming all metals pass through the turbine. 64 The average fuel analysis result 
can be used to calculate emissions based on fuel usage or stack exhaust flow measurements. 
Potential emissions based on the trace element content of distillate oils have been calculated and 
compared with measured stack emissions. 65 In almost all cases, the potential emissions were 
higher than the measured emissions. An emission factor for distillate oil-fired turbines is 
presented in Table 4-20. 64 


4-78 


TABLE 4-18. ARSENIC EMISSION FACTOR FOR CREMATORIES 


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4-79 










TABLE 4-19. 1991 U.S. CREMATORY LOCATIONS BY STATE 


State 

No. of 
Crematories 

No. of 
Cremations 

State 

No. of 
Crematories 

No. of 
Cremations 

Alabama 

6 

1,313 

Montana 

15 

3,234 

Alaska 

6 

860 

Nebraska 

7 

1,710 

Arizona 

31 

13,122 

Nevada 

12 

6,343 

Arkansas 

13 

2,435 

New Hampshire 

6 

2,348 

California 

142 

89,233 

New Jersey 

16 

16,557 

Colorado 

27 

9,537 

New Mexico 

10 

3,140 

Connecticut 

10 

5,528 

New York 

38 

24,625 

Delaware 

4 

1,062 

North Carolina 

27 

6,884 

District of Columbia 

0 

- 

North Dakota 

1 

- 

Florida 

97 

59,213 

Ohio 

42 

16,109 

Georgia 

15 

4,786 

Oklahoma 

10 

2,120 

Hawaii 

8 

3,937 

Oregon 

36 

11,272 

Idaho 

13 

2,637 

Pennsylvania 

46 

16,867 

Illinois 

47 

17,557 

Rhode Island 

5 

2,446 

Indiana 

25 

4,743 

South Carolina 

12 

2,422 

Iowa 

14 

3,042 

South Dakota 

3 

- 

Kansas 

10 

2,029 

Tennessee 

9 

2,451 

Kentucky 

6 

1,548 

Texas 

39 

13,795 

Louisiana 

5 

2,466 

Utah 

6 

1,210 

Maine 

4 

3,469 

Vermont 

5 

1,902 

Maryland 

18 

6,300 

Virginia 

26 

7,738 

Massachusetts 

13 

10,611 

Washington 

49 

18,466 

Michigan 

40 

17,460 

West Virginia 

6 

762 

Minnesota 

20 

7,296 

Wisconsin 

28 

7,293 

Mississippi 

4 

693 

Wyoming 

3 

- 

Missouri 

23 

6,105 





Source: Reference 63. 


4-80 











TABLE 4-20. ARSENIC EMISSION FACTORS FOR INTERNAL COMBUSTION ENGINES 


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4-81 










4.7.2 Source Description 


Internal combustion sources for electricity generation and industrial application are 
grouped into two types: gas turbines and reciprocating engines.. 

Stationary gas turbines are applied in electric power generators, in gas pipeline pump and 
compressor drives, and various process industries. Gas turbines greater than 3 MW are used in 
electric generation for continuous, peaking, or standby power. The primary fuels used are natural 
gas and distillate (No. 2) fuel oil. 64 

Reciprocating internal combustion engines may be classified as spark ignition and 
compression ignition. Spark ignition engines are fueled by volatile liquids such as gasoline, 
whereas compression ignition engines use liquid fuels of low volatility, such as kerosene and 
distillate oil (diesel fuel). 65 

In compression ignition engines, combustion air is compression-heated in the cylinder 
and diesel fuel oil is then injected into this hot air. Ignition is spontaneous because the air is 
above the autoignition temperature of the fuel. Spark ignition engines initiate combustion with 
an electrical discharge. Usually, fuel is mixed with air in a carburetor (for gasoline) or at the 
intake valve (for natural gas), but fuel can also be injected directly into the cylinder. 66 

The rated power of gasoline and diesel internal combustion engines covers a substantial 
range: up to 250 hp for gasoline engines and up to and greater than 600 hp for diesel engines. 

The primary domestic use of large stationary diesel engines (greater than 600 hp) is in oil and gas 
exploration and production. These engines supply mechanical power to operate drilling (rotary 
table), mud pumping, and hoisting equipment and may also operate pumps or auxiliary power 
generators. 67 Stationary natural gas-fired spark ignition engines of over 5,000 hp and natural 
gas-fired turbines of over 10,000 hp exist. 


4-82 


References for Section 4.0 


1. National Research Council. Particulate Polycyclic Organic Matter. Washington, D.C.: 
Committee on Biologic Effects of Atmospheric Pollutants, Division of Medical Sciences, 
National Academy of Sciences, 1972. 

2. National Research Council. Polycyclic Aromatic Hydrocarbons: Evaluation of Sources 
and Effects. Washington, D.C.: Committee on Pyrene and Selected Analogues, Board on 
Toxicology and Environmental Health Hazards, Commission on Life Sciences, National 
Academy Press, 1983. 

3. Khan, R.M. Clean Energy from Waste and Coal. Developed from a symposium 
sponsored by the Division of Fuel Chemistry of the 202 nd National Meeting of the 
American Chemical Society. New York, New York: August 29-30, 1991. 

4. U.S. EPA. Locating and Estimating Air Toxic Emissions from Medical Waste 
Incinerators. EPA-454/R-93-053. Research Triangle Park, North Carolina: 

5. U.S. EPA. Correlation of Coal Properties with Environmental Control Technology 
Needs for Sulfur and Trace Elements. Contract No. 68-02-3171. Research Triangle Park, 
North Carolina: U.S. Environmental Protection Agency, Industrial Environmental 
Research Laboratory, 1983. 

6. U.S. EPA. Alternative Control Techniques Document - NO x Emissions from Utility 
Boilers. EPA-453/R-94-023. Research Triangle Park, North Carolina: 

U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, 
March 1994. 

7. Shih, C.C. et al. Emissions Assessment of Conventional Stationary Combustion 
Systems , Volume EE: External Combustion Sources for Electricity Generation. 
EPA-600/7-81-003a. Washington, D.C.: U.S. Environmental Protection Agency, Office 
of Research and Development, November 1980. pp. 455. 

8. U.S. EPA. Compilation of Air Pollutant Emission Factors , 5th ed. (AP-42), Vol. I: 
Stationary Point and Area Sources, Section 1.1: Bituminous and Subbituminous Coal 
Combustion. Research Triangle Park, North Carolina: U.S. Environmental Protection 
Agency, Office of Air Quality Planning and Standards, 1995. 

9. Kelly, M.E. Sources and Emissions of Polycyclic Organic Matter. EPA 450/5-83-010b. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 1983. 
pp. 5-9 to 5-44. 

10. Mead, R.C., G.W. Brooks, and B.K. Post. Summary of Trace Emissions from and 
Recommendations of Risk Assessment Methodologies for Coal and Oil Combustion 
Sources. EPA Contract No. 68-02-3889, Work Assignment 41. Research Triangle Park, 


4-83 


North Carolina: U.S. Environmental Protection Agency, Pollutant Assessment Branch, 
July 1986. 

11. U.S. EPA. Fossil Fuel Fired Industrial Boilers - Background Information , Volume 1, 
Chapters 1 to 9. EPA-450/3-82-006a. Research Triangle Park, North Carolina: 

U.S. Environmental Protection Agency, March 1982. 

12. AP-42, 5th ed., op. cit ., note 8. Section 1.6: Wood Waste Combustion in Boilers, 1995. 

13. U.S. EPA. Population and Characteristics of Industrial/Commercial Boilers in the 
United States . EPA-600/7-79-178a. Research Triangle Park, North Carolina: 

U.S. Environmental Protection Agency, Industrial Environmental Research Laboratory, 
August 1979. pp. 6-37. 

14. Buonicore, A.J. and W.T. Davis, eds. Air Pollution Engineering Manual. New York: 
Air and Waste Management Association, 1992. pp. 257-260. 

15. AP-42, 5th ed., op. cit., note 8. Section 1.11: Waste Oil Combustion, 1995. 

16. NRDC. Burning Used Oil - America's Undiscovered Lead Threat. National Resources 
Defense Council, 1991. 

17. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, 

Pan 261-Identification and Listing of Hazardous Waste, Subpart A—General, 

Section 261.6-Requirements for Recylcable Materials. Washington, D.C.: 

U.S. Government Printing Office, July 1994. p. 43. 

18. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, 

Part 279-Standards for the Management of Used Oil, Subpart A—Applicability, 

Section 279.11-Used Oil Specifications. Washington, D.C.: U.S. Government Printing 
Office, July 1994. p. 861. 

19. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, 

Pan 279-Standards for the Management of Used Oil, Subpart C~Standards for Used Oil 
Generators, Section 279.23—On-Site Burning in Space Heaters. Washington, D.C.: 

U.S. Government Printing Office, July 1994. p. 863. 

20. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, 

Pan 279-Standards for the Management of Used Oil, Subpan G--Standards for Used Oil 
Burners who Bum Off-Specification Used Oil for Energy Recovery. Washington, D.C.: 
U.S. Government Printing Office, July 1994. pp. 877 to 880. 

21. California Air Resources Board. Results of Source Testing at a Power Production 
Facility. Confidential Report No. ERC-83. November 8, 1991. 


4-84 


22. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 711. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

23. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 709. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

• 

24. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 1054. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

25. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 706. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

26. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 714. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

27. California Air Resources Board. Determination of AB 2588 emissions from wood-fired 
boiler exhaust. Confidential Report No. ERC-63. February 10 - 13, 1992. 

28. AP-42, 5th ed., op. cit., note 8. Section 1.2: Anthracite Coal Combustion, 1995. 

29. AP-42, 5th ed., op. cit., note 8. Section 1.7: Lignite Combustion, 1995. 

30. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 189. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

31. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 215. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

32. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 220. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

33. AP-42, 5th ed., op. cit., note 8. Section 1.3: Fuel Oil Combustion, 1995. 

34. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 705. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 


4-85 



35. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 243. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

36. California Air Resources Board. Results of Source Testing at a Waste Converter Facility. 
Confidential Report No. ERC-118. September 26-28, 1990. 

37. U.S. EPA. Locating and Estimating Air Emissions from Sources of Polycyclic Organic 
Matter (POM). EPA-450/4-84-007p. Research Triangle Park, North Carolina: 

U.S. Environmental Protection Agency, September 1987. 

38. Air & Waste Management Association. Air Pollution Engineering Manual , 

AJ. Buonicore and W. Davis, eds. New York, New York: Van Nostrand Reinhold, 

1992. 

39. Oppelt, E.T. Incineration of Hazardous Waste - A Critical Review. Journal of Air 
Pollution Control Association. 37(5):558-586, May 1987. 

40. Vogel, G., et al (Mitre Corp). Composition of Hazardous Waste Streams Currently 
Incinerated. U.S. Environmental Protection Agency, April 1983. 

41. U.S. EPA. Permit Writer's Guide to Test Bum Data - Hazardous Waste Incineration. 
EPA-625/6-86-012. Washington, D.C.: U.S. Environmental Protection Agency, Office 
of Research and Development, 1986. 

42. Whitworth, W.E. and L.E. Waterland. Pilot-Scale Incineration of PCB-Contaminated 
Sediments from the Hot Spot of the New Bedford Harbor Superfund Site. Jefferson, 
Arkansas: Acurex Corporation, January 1992. 

43. Niessen, W.R. and R.C. Porter. Methods for Estimating Trace Metal Emissions from 
Fluidized Bed Incinerators using Advanced Air Pollution Control Equipment. Air and 
Waste. 8:2-3, 1991. 

44. California Air Resources Board. Results of Source Testing at a Chemical Waste 
Management Facility. Confidential Report No. ERC-108. May 25, 1990. 

45. Rigo, H.G. Rigo & Associates, Inc. Berea, Ohio. Teleconference with Phil Marsosudiro. 
Eastern Research Group, Morrisville, North Carolina. March 30, 1998. 

46. AP-42, 5th ed., op. cit., note 8. Section 2.1: Refuse Combustion, 1995. 

47. Standards of Performance for New Stationary Sources, Municipal Waste Combustors, 54 
FR 243 IV(f), December 20, 1989. 


4-86 


48. World Health Organization. Emissions of Heavy Metal and PAH Compounds from 
Municipal Solid Waste Incinerators. Control Technology and Health Effects. 
Copenhagen, Denmark: World Health Organization, Regional Office for Europe, 1988. 

49. Integrated Waste Services Association. Municipal Waste Combustor Directory 
1997-1998, Washington, D.C. October, 1997. 

50. AP-42, 5th ed., op. cit., note 8. Section 2.2: Sewage Sludge Incineration, 1995. 

51. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 234. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

52. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 101. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

53. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 101. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

54. U.S. EPA. Locating and Estimating Air Toxics Emissions from Sewage Sludge 
Incinerators. EPA-450/2-90-009. Research Triangle Park, North Carolina: 

U.S. Environmental Protection Agency, 1990. 

55. AP-42, 5th ed., op. cit., note 8. Section 2.3: Medical Waste Incineration, 1995. 

56. EPA-450/R-97-007. Hospital/Medical/Infectious Waste Incineration Emission 
Guidelines: Summary of the requirements for Section 1 ll(d)/129 State Plans. 

U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, 
Research Triangle Park, North Carolina. November, 1997. 

57. Huffman, G.L. and C.C. Lee. Metal Behavior During Medical Waste Incineration. ACS 
Symposium Series Clean Energy from Waste and Coal, Chapter 15. August 1991. 

pp. 189-194. 

% 

58. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 167. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

59. California Air Resources Board. Results of Source Testing at a Medical Waste 
Incinerator. Confidential Report No. ERC-114. August 1991. 

60. U.S. Environmental Protection Agency. Fact Sheet —Air Emission Standards and 
Guidelines for HosptaUMedicaUInfectious Waste Incinerators. August 15, 1997. 


4-87 



61. Springer, J.M. (Executive Director, Cremation Association of North America). Personal 
correspondence to Dennis Beauregard (Emission Factor Inventory Group, 

U.S. Environmental Protection Agency). January 31, 1996. 

62. California Air Resources Board. Results of Source Testing of a Propane-fired 
Incinerator at a Crematorium. Confidential Report No. ERC-39. October 29, 1992. 

63. Cremation Association of North America. Cremation Statistics. Cremationist. Chicago, 
Illinois: Cremation Association of North America, 1994. 

64. AP-42, 5th ed., op cit ., note 8. Section 3.1, Stationary Gas Turbines for Electricity 
Generation, 1995. 

65. U.S. EPA. Emissions Assessment of Conventional Stationary Combustion Systems, 

Vol. D: Internal Combustion Sources. EPA-600/7-79-029c. Research Triangle Park, 
North Carolina: Industrial Environmental Research Laboratory, U.S. Environmental 
Protection Agency, February 1979. 

66. AP-42, 5th ed., op cit., note 8. Section 3.3, Gasoline and Diesel Industrial Engines, 1995. 

67 AP-42, 5th ed., op cit., note 8. Section 3.4, Large Stationary Diesel and All Stationary 

Dual Fuel Engines, 1995. 


4-88 


SECTION 5.0 




EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM THE 

METALLURGICAL INDUSTRY 

5.1 Primary Lead Smelting 

Lead is recovered from a sulfide ore, primarily galena (lead sulfide [PbS]), which also 
contains small amounts of copper, iron, zinc, and other trace elements. Arsenic typically appears 
in the form of arsenopyrite (FeAsS) or arsenic sulfide (AS 2 S 3 ) in lead-bearing ore. A description 
of the process used to manufacture lead and a discussion of the emissions resulting from the 
various operations are presented below. 

A list of primary lead smelters currently in operation within the United States is given in 
Table 5-1. Primary lead smelters produced 449,800 tons of refined lead in 1990. 1 

5.1.1 Process Description 

Figure 5-1 presents a typical process flow diagram for primary lead smelting. The 
recovery of lead from the lead ore consists of three main steps: sintering, reduction, and 
refining. 2 

Sintering is carried out in a sintering machine, which is a continuous steel pallet conveyor 
belt. Each pallet consists of perforated grates, and beneath the grates are wind boxes, which are 
connected to fans to provide a draft through the moving sinter charge. Depending on the 
direction of the draft, the sinter machine is characterized as either an updraft or downdraft 


5-1 








TABLE 5-1. DOMESTIC PRIMARY LEAD SMELTERS AND REFINERIES 


Smelter 

Refinery 

1990 Production 

tons 

ASARCO, East Helena, MT 

ASARCO, Omaha, NE a ' 

72,500 

ASARCO, Glover, MO 

Same site 

123,200 

Doe Run (formerly St. Joe), 

Same site 

254,100 

Herculaneum, MO 


- 


Source: Reference 1. 
a Scheduled to be closed. 


machine. Except for the draft direction, all machines are similar in design, construction, and 
operation. Capacities range from 1,000 to 2,500 tons per day. Lead concentrates account for 
30 to 35 percent of the input material for the sintering process. The balance of the charge 
consists of fluxes such as limestone and large amounts of recycled sinter or smelter residues. 3 

The blast furnace reduces the lead oxide produced in the sintering machine to elemental 
lead and removes undesirable impurities as a slag. Reduction reactions to elemental lead occur 
around 2,900°F. The resulting metal, called bullion, assays 94 to 98 percent lead. The furnace is 
a rectangular, water-cooled steel shell or shaft atop a refractory lined crucible or hearth. Both 
sides are equipped with tuyeres through which pressurized combustion or blast air is introduced. 
Furnace capacities range from 500 to 1,000 tons per day. The charge to the furnace includes 
sinter, coke, slags from drossing and refining processes, silica, limestone, and baghouse dust. 
About 80 percent of the charge consists of sinter that may contain from 28 to 50 percent lead. 
Blast air is introduced through the side-mounted tuyeres resulting in partial combustion of coke 
and formation of carbon monoxide and providing the heat required to reduce lead oxide to lead 
bullion. Most of the impurities react with the silica and limestone and form a slag. The slag is 
skimmed continuously from the furnace and is treated either at the smelter or is shipped 
elsewhere to recover the metal content. Slags that are high in zinc are generally treated at the 
smelter in a zinc forming furnace to recover zinc oxide. 3 


5-2 







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Figure 5-1. Typical Primary Lead-Processing Scheme 



































































































































































The lead bullion is tapped from the furnace periodically, and is usually treated in a 
drossing kettle before undergoing final refining. In the kettle, the bullion is cooled and the higher 
melting impurities, primarily copper, float to the surface and form a dross which is skimmed off 
and subsequently treated in a reverberatory furnace. The bullion undergoes a final refining in a 
series of cast iron kettles. The final lead product, typically 99.99 percent or more pure, is then 
cast into pigs or ingots for shipping. 

The function of the dross reverberatory furnace is to separate lead bullion carried over in 
the dross from other metals of economic value or contaminants in the dross. The dross lead 
content may be as high as 90 percent. Although much smaller, the reverberatory furnace used is 
similar in construction to the reverberatory furnace used in copper smelting. Where applied, 
end-products usually include lead bullion, which is recycled, matte, which is rich in copper and 
usually sent to a copper smelter for copper recovery, and speiss, which is high in arsenic and 
antimony. 3 

5.1.2 Emission Control Techniques 

Emission controls on primary lead smelter operations are used for controlling particulate 
matter (PM) and sulfur dioxide (S0 2 ) emissions resulting from the blast furnace and sintering 
machines. Centrifugal collectors (cyclones) may be used in conjunction with fabric filters or 
electrostatic precipitators (ESPs) for PM control. In addition, fugitive emissions from the 
drossing kettles are typically controlled by building enclosure or kettle hooding systems. 3 There 
were no arsenic removal efficiency tests available to determine the exact removal efficiencies of 
the typical control devices used at primary lead smelting facilities. However, it has been 
estimated by analogy to copper smelting data, that arsenic removal efficiencies greater than 
90 percent can be achieved by fabric filter systems and that the “best available” ventilation 
capture systems used to control fugitive emissions are capable of approximately 90 percent 
fugitive emission control. 3 


5-4 


5.1.3 Emissions 


Most of the arsenic entering with the plant feed (>80 percent) can be accounted for in the 
solid products leaving a facility. 4 Arsenic can potentially be emitted from each unit operation 
within a primary lead smelting facility. Arsenic removal from the lead-bearing portion of the 
charge material includes volatilization, slagging, and an association with the matte and speiss 
phases (mixture of impure metallic arsenides) that are ultimately shipped to copper smelters. 
Typically, arsenic will be emitted as PM. If any particle size partitioning occurs, it is generally 
found that arsenic is most likely to be associated with the finer particles. 4 

In addition, for processes where the operating temperature is near the boiling point of 
arsenic, arsenic fumes may be emitted. For example, arsenic can be volatilized as arsenic 
trioxide from sinter plants, blast furnaces, dross reverberatory furnaces, zinc fuming furnaces, 
and reverberatory softening furnaces (lead refining). 4 One study from a Missouri lead smelter 
determined that approximately 12.9 percent of the arsenic entering a smelter was unaccounted for 
in the solid waste and product streams. The study concluded that this figure represented the 
approximate amount that was emitted to the atmosphere. 4 Table 5-2 presents an arsenic emission 
factor that may be used for estimating arsenic emissions from an entire primary lead smelting 
operation 4 The reader is cautioned that this emission factor represents a rough estimate only and 
the quality of the factor is uncertain. 

5.2 Secondary Lead Smelting 

5.2.1 Process Description 

The secondary lead smelting industry produces elemental lead and lead alloys by 
reclaiming lead, mainly from scrap automobile batteries. Blast, reverberatory, rotary, and electric 
furnaces are used for smelting scrap lead and producing secondary lead. Smelting is the 


5-5 



TABLE 5-2. ARSENIC EMISSION FACTOR FOR PRIMARY LEAD SMELTING FACILITIES 


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reduction of lead compounds to elemental lead in a high-temperature furnace, which requires 
higher temperatures (2,200 to 2,300°F) than those required for melting elemental lead (621 °F). 
Secondary lead may be refined to produce soft lead (which is nearly pure lead) or alloyed to 
produce hard lead. Most of the lead produced by secondary lead smelters is used in the 
production of lead-acid batteries. 5 

Lead-acid batteries represent about 90 percent of the raw materials at a typical secondary 
lead smelter, although this percentage may vary from one plant to the next. These batteries 
contain approximately 18 lb of lead per battery consisting of 40 percent lead alloys and 
60 percent lead oxide. Other types of lead-bearing raw materials recycled by secondary lead 
smelters include drosses (lead-containing byproducts of lead refining), which may be purchased 
from companies that perform lead alloying or refining but not smelting; battery plant scrap, such 
as defective grids or paste; and scrap lead, such as old pipes or roof flashing. Other scrap lead 
sources include cable sheathing, solder, and babbitt-metal. 5 

As illustrated in Figure 5-2, the normal sequence of operations in a secondary lead 
smelter is scrap receiving, charge preparation, furnace smelting, and lead refining, alloying, and 
casting.' In the majority of plants, scrap batteries are first sawed or broken open to remove the 
lead alloy plates and lead oxide paste material. The removal of battery covers is typically 
accomplished using an automatic battery feed conveyor system and a slow-speed saw. Hammer 
mills or other crushing/shredding devices are then used to break open the battery cases. 
Float/sink separation systems are typically used to separate plastic battery parts, lead terminals, 
lead oxide paste, and rubber parts. The majority of lead smelters recover the crushed plastic 
materials for recycling. Rubber casings are usually landfilled or incinerated in the smelting 
furnace for their fuel value, and in many cases, lead is reclaimed from the castings. 

Paste desulfurization, an optional lead recovery step used by some secondary lead 
smelters, requires the separation of lead sulfate and lead oxide paste from the lead grid metal, 
polypropylene plastic cases, separators, and hard rubber battery cases. Paste desulfurization 


5-7 


Batteries Arrive 
by Truck 




Disposal 


T 

Finished 

Product 


Figure 5-2. Simplified Process Flow Diagram for Secondary Lead Smelting 
Source: Reference 5. 


5-8 



























involves the chemical removal of sulfur from the lead battery paste. The process improves 
furnace efficiency by reducing the need for fluxing agents to reduce lead-sulfur compounds to 
lead metal. The process also reduces S0 2 furnace emissions. However, S0 2 emissions reduction 
is usually a less important consideration because many plants that perform paste desulfurization 
are also equipped with S0 2 scrubbers. About one-half of smelters perform paste 
desulfurization. 5 

After removing the lead components from the batteries, the lead scrap is combined with 
other charge materials such as refining drosses and flue dust which are charged to a reverberating 
furnace. Reverberating furnace slag, coke, limestone, sand, and scrap iron are fed to a blast, 
rotary or electric smelting furnace. Smelting furnaces are used to produce crude lead bullion, 
which is refined and/or alloyed into final lead products. In 1994 there were approximately 
14 reverberatory furnaces, 24 blast furnaces, 5 rotary furnaces, and 1 electric furnace operating in 
the secondary lead industry in the United States. 5 Blast and reverberatory furnaces are currently 
the most common types of smelting furnaces used in the industry, although some new plants are 
using rotary furnaces. 

Reverberatory Furnaces 

A reverberatory furnace (Figure 5-3) is a rectangular refractory-lined furnace operated on 
a continuous basis. 5 Natural gas- or fuel oil-fired jets located at one end or at the sides of the 
furnace are used to heat the furnace and charge material to an operating temperature of about 
2,200 to 2,300°F. 5 Oxygen enrichment may be used to decrease the combustion air 
requirements. Reverberatory furnaces are maintained at negative pressure by an induced draft 
fan. 


Reverberatory furnace charge materials include battery grids and paste, battery plant 
scrap, rerun reverberatory furnace slag, flue dust, drosses, iron, silica, and coke. A typical charge 
over one hour may include 9.3 tons of grids and paste to produce 6.2 tons of lead. 5 


5-9 


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Charge materials are often fed to a natural gas- or oil-fired rotary drying kiln, which dries 
the material before it reaches the furnace. The temperature of the drying kiln is about 400°F, and 
the drying kiln exhaust is drawn directly into the reverberatory furnace or ventilated to a control 
device. From the rotary drying kiln, the feed is either dropped into the top of the furnace through 
a charging chute, or fed into the furnace at fixed intervals with a hydraulic ram. In furnaces that 
use a feed chute, a hydraulic ram is often used as a stoker to move the material down the furnace. 

Reverberatory furnaces are used to produce a soft, nearly pure lead product and a 
lead-bearing slag. This is done by controlling the reducing conditions in the furnace so that lead 
components are reduced to metallic lead bullion while the alloying elements (antimony, tin, 
arsenic) in the battery grids, posts, straps, and connectors are oxidized and removed in the slag. 
The reduction of PbS0 4 and PbO is promoted by the carbon-containing coke added to the charge 
material: 

PbS0 4 + C - Pb + C0 2 + S0 2 

The PbS0 4 and PbO also react with the alloying elements to forni lead bullion and oxides of the 
alloying elements, which are removed in the slag. 

The molten lead collects in a pool at the lowest part of the hearth. Slag collects in a layer 
on top of this pool and retards further oxidation of the lead. The slag is made up of molten 
fluxing agents such as iron, silica, and lime, and typically has significant quantities of lead. Slag 
is usually tapped continuously and lead is tapped intermittently. The slag is tapped into a mold. 
The slag tap and mold are hooded and vented to a control device. Reverberatory furnace slag 
usually has a high lead content (as much as 70 percent by weight) and is used as feed material in 
a blast or electric furnace to recover the lead. Reverberatory furnace slag may also be rerun 
through the reverberatory furnace during special slag campaigns before being sent to a blast or 
electric furnace. Lead may be tapped into a mold or directly into a holding kettle. The lead tap is 
usually hooded and vented to a control device.^ 


5-11 


Blast Furnaces 


A blast furnace (Figure 5-4) is a vertical furnace that consists of a crucible with a vertical 
cylinder affixed to the top. 5 The crucible is refractory-lined and .the vertical cylinder consists of a 
steel water-jacket. Oxygen-enriched combustion air is introduced into the furnace through 
tuyeres located around the base of the cylinder. 

Charge materials are pre-weighed to ensure the proper mixture and then are introduced 
into the top of the cylinder using a skip hoist, a conveyor, or a front-end loader. The charge fills 
nearly the entire cylinder. Charge material is added periodically to keep the level of the charge at 
a consistent working height while lead and slag are tapped from the crucible. Coke is added to 
the charge as the primary fuel, although natural gas jets may be used to start the combustion 
process. Combustion is self-sustaining as long as there is sufficient coke in the charge material. 
Combustion occurs in the layer of the charge nearest the tuyeres. 

At plants that operate only blast furnaces, the lead-bearing charge materials may include 
broken battery components, drosses from the refining kettles, agglomerated flue dust, and 
lead-bearing slag. A typical charge over one hour may include 4.8 tons of grids and paste, 

0.3 tons of coke. 0.1 tons of calcium carbonate, 0.07 tons of silica, 0.5 tons of cast iron, and 
0.2 tons of rerun blast furnace slag, to produce 3.7 tons of lead. At plants that also have a 
reverberatory furnace, the charge materials will also include lead-bearing reverberatory furnace 
slag. 5 


Blast furnaces are designed and operated to produce a hard (high alloy content) lead 
product by achieving greater furnace reduction conditions than those typically found in a 
reverberatory furnace. Fluxing agents include iron, soda ash, limestone, and silica (sand). The 
oxidation of the iron, limestone, and silica promotes the reduction of lead compounds and 
prevents oxidation of the lead and other metals. The soda ash enhances the reaction of PbS0 4 
and PbO with carbon from the coke to reduce these compounds to lead metal. 


5-12 


Charge Hopper 


Charge 


Cool Water 


Hot Water 


Cool Water 


Exhaust Offtake to Afterburner 


Average Level of Charge 


Working Height 
of Charge 
2.4 to 3.0 m 


Lead Spout 



Slag Layer 


Figure 5-4. Cross-Section of a Typical Blast Furnace 


Source: Reference 5. 


5-13 


ERG_Lead_44.pre 




























































































Lead tapped from a blast furnace has a higher content of alloying metals (up to 
25 percent) than lead produced by a reverberatory furnace. In addition, much less of the lead and 
alloying metals are oxidized and removed in the slag, so the slag has a low metal content (e.g., 

1 to 3 percent) and may qualify as a nonhazardous solid waste. . 

Because air is introduced into the blast furnace at the tuyeres, blast furnaces are operated 
at positive pressure. The operating temperature at the combustion layer of the charge is between 
2,200 and 2,600°F, but the temperature of the gases exiting the top of the charge material is only 
between 750 and 950°F. 

Molten lead collects in the crucible beneath a layer of molten slag. As in a reverberatory 
furnace, the slag inhibits the further oxidation of the molten metal. Lead is tapped continuously 
and slag is tapped intermittently, slightly before it reaches the level of the tuyeres. If the tuyeres 
become blocked with slag, they are manually or automatically “punched” to clear the slag. A 
sight glass on the tuyeres allows the furnace operator to monitor the slag level and ensure that the 
tuyeres are clear of slag. At most facilities, the slag tap is temporarily sealed with a clay plug, 
which is driven out to begin the flow of slag from the tap into a crucible. The slag tap and 
crucible are enclosed in a hood, which is vented to a control device. 

A weir dam and siphon in the furnace are sometimes used to remove the lead from 
beneath the slag layer. Lead is tapped from a blast furnace into either a crucible or directly to a 
refining kettle designated as a holding kettle. The lead in the holding kettle is kept molten before 
being pumped to a refining kettle for refining and alloying. The lead tap on a blast furnace is 
hooded and vented to a control device. 

Rotary Furnaces 

As noted above, rotary furnaces (sometimes referred to as rotary reverberatory furnaces) 
(Figure 5-5) are used at only a few recently constructed secondary lead smelters in the 


5-14 


Hygiene Hood 



Drive Train 


Figure 5-5. Side View of a Typical Rotary Reverberatory Furnace 
Source: Reference 5. 


5-15 


ejd S* OV31~Dd3 



















































































































United States. 5 Rotary furnaces have two advantages over other furnace types: the ease of 
adjusting the relative amount of fluxing agents (because the furnaces are operated on a batch 
rather than a continuous basis), and better mixing of the charge materials. 

A rotary furnace consists of a refractory-lined steel drum mounted on rollers with a 
variable-speed motor to rotate the drum. An oxygen-enriched natural gas or fuel oil jet at one 
end of the furnace heats the charge material and the refractory lining of the drum. The 
connection to the flue is located at the same end as the jet. A sliding door at the end of the 
furnace opposite the jet allows charging of material to the furnace. Charge materials are typically 
placed in the furnace using a retractable conveyor or charge bucket, although other methods are 
possible. 

Lead-bearing raw materials charged to rotary furnaces include broken battery 
components, flue dust, and drosses. Rotary furnaces can use the same lead-bearing raw materials 
as blast furnaces. They usually produce slag that is relatively free of lead, less than 2 percent. A 
rotary furnace can be used instead of a blast furnace. 

Fluxing agents for rotary furnaces may include iron, silica, soda ash, limestone, and coke. 
The fluxing agents are added to promote the conversion of lead compounds to lead metal. Coke 
is used as a reducing agent rather than as a primary fuel. A typical charge may consist of 12 tons 
of wet battery scrap, 0.8 tons of soda ash, 0.6 tons of coke, and 0.6 tons of iron, and will yield 
approximately 9 tons of lead product. 5 

The lead produced by rotary furnaces is a semi-soft lead with an antimony content 
somewhere between that of lead from reverberatory and blast furnaces. Lead and slag are tapped 
from the furnace at the conclusion of the smelting cycle. Each batch takes 5 to 12 hours to 
process, depending on the size of the furnace. Like reverberatory furnaces, rotary furnaces are 
operated at a slight negative pressure. 


5-16 


Electric Furnaces 


An electric furnace consists of a large, steel, kettle-shaped container that is 
refractory-lined (Figure 5-6). 5 A cathode extends downward into the container and an anode is 
located in the bottom of the container. Second-run reverberatory furnace slag is charged into the 
top of the furnace. Lead and slag are tapped from the bottom and side of the furnace, 
respectively. A fume hood covering the top of the furnace is vented to a control device. In an 
electric furnace, electric current flows from the cathode to the anode through the scrap charge. 
The electrical resistance of the charge causes the charge to heat up and become molten. There is 
no combustion process involved in an electric furnace. 

There is only one known electric furnace in operation in the U.S. for the secondary lead 
industry. It is used to process second-run reverberatory furnace slag, and it fulfills the same role 
as a blast furnace used in conjunction with a reverberatory furnace. However, the electric 
furnace has two advantages over a blast furnace. First, because there are no combustion gases, 
ventilation requirements are much lower than for blast or reverberatory furnaces. Second, the 
electric furnace is extremely reducing, and produces a glass-like, nearly lead-free slag that is 
nonhazardous. 5 

Refining, the final step in secondary lead production, consists of removing impurities and 
adding alloying metals to the molten lead obtained from the smelting furnaces to meet a 
customer’s specifications. Refining kettles are used to purify and alloy molten lead. 

5.2.2 Emission Control Techniques 

Control devices at secondary smelters are primarily aimed at controlling S0 2 and PM 
emissions. Control devices used to control furnace operation emissions include baghouses and 
scrubbers. Typically, baghouses are preceded by an afterburner and cooler when applied on a 
blast furnace and a cooler alone when used on a reverberatory furnace. Scrubbers installed after 


5-17 


Electrode 


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5-18 


Figure 5-6. Cross-Sectional View of an Electric Furnace for Processing Slag 













































































baghouses are primarily aimed at controlling S0 2 emissions. Hooding and ventilation to 
baghouses are commonly used to control process fugitive emissions. Nonprocess fugitive 
emissions can be controlled by implementing wetting techniques, as well as enclosure of storage 
piles. 


Certain work practices and personal protection strategies can be implemented to reduce 
worker arsenic exposure. These include housekeeping, administrative controls, and the use of 
respirators, gloves, goggles, and aprons. 6 

5.2.3 Emissions 

In secondary lead smelting operations, arsenic can be emitted in some degree from each 
process unit. In addition, there can be fugitive arsenic emissions from both process and 
nonprocess sources. In general, arsenic emissions vary with the amount of arsenic in the feed 
material, the operating conditions of the furnace, the amount of chlorides in the feed material, 
and the slag composition. Arsenic emission factors for secondary lead smelting are presented in 
Table 5-3. 4 - 7 - 8 - 9 

The primary sources of process emissions are the smelting furnace and the refining kettle. 
Arsenic is present in several of the furnace feed materials and in all of the furnace products 4 
The amount of arsenic in the feed material may vary greatly. In smelting operations, 
arsenic-containing materials are subjected to high furnace temperatures and either oxidizing or 
reducing temperatures. In certain oxidizing environments (e.g., reverberatory furnaces), arsenic 
trioxide can be formed and subsequently vaporize and leave with the offgases. In addition, 
arsenic can become complexed in the slag and exit the furnace with this stream. 

The three main sources of process fugitive arsenic emissions are the charging operation, 
the slag tapping operation, and the metal pouring operation. As expected, the magnitude of 
arsenic emissions would vary with the arsenic content of the charge material. Emissions from 


5-19 


TABLE 5-3. ARSENIC EMISSION FACTORS FOR SECONDARY LEAD SMELTING FACILITIES 






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5-20 











the charging operationanclude fine particulates and fumes, originating from recycled flue dusts 
which can contain significant amounts of arsenic. The slag and metal tapping operations 
incorporate high temperatures and therefore generate a considerable amount of fumes. Those 
fumes that are not captured and controlled represent process fugitive emissions. 

Fugitive nonprocess arsenic emissions will be affected by the arsenic content of the 
various fine materials being stored at the smelter including the non-agglomerated flue dusts and 
the dried battery mud. The flue dust storage pile in the charge preparation area is the primary 

source of nonprocess fugitive arsenic emissions at a secondary lead smelting facility. 4 In 

» 

addition, battery breaking yards, battery storage areas, slag storage areas, and smelter access 
roads have all been identified as potential sources of nonprocess fugitive arsenic emissions. 
Meteorological factors (in particular the amount of wind and rain) and the amount of activity 
around the plant site can influence the total amount of arsenic from this source. 4 

5.2.4 Source Locations 

In 1990, primary and secondary smelters in the United States produced 1,380,000 tons of 
lead. Secondary lead smelters produced 946,000 tons or about 69 percent of the total refined lead 
produced in 1990. 5 Table 5-4 lists U.S. secondary lead smelters according to their annual lead 

production capacity. 5 

5.3 Primary Copper Production 

5.3.1 Source Description 

Seven primary copper smelters were operating in the United States in 1995 and one more 
was closed for modifications. The combined production capacity in 1995 for the seven plants in 
operation was 1,728,043 tons. 10 


5-21 


TABLE 5-4. U.S. SECONDARY LEAD SMELTERS GROUPED ACCORDING TO 

ANNUAL LEAD PRODUCTION CAPACITY 


Smelter 

Location 

Small-Capacitv Group:* 


Delatte Metals b 

Ponchatoula, LA 

General Smelting and Refining Company 

College Grove, TN 

Master Metals, Inc. b 

Cleveland, OH 

Metals Control of Kansas b 

Hillsboro, KS 

Metals Control of Oklahoma b 

Muskogee, OK 

Medium-CaDacitv Qpoup: c 

* 

Doe Run Company 

Boss, MO 

East Penn Manufacturing Company 

Lyon Station, PA 

Exide Corporation 

Muncie, IN 


Reading, PA 

GNB, Inc. 

Columbus, GA 


Frisco, TX 

Gulf Coast Recycling, Inc. 

Tampa, FL 

Refined Metals Corporation 6 

Beech Grove, IN 


Memphis, TN 

RSR Corporation 

City of Industry, CA 


Middletown, NY 

Schuylkill Metals Corporation 

Forest City, MO 

Texas Resources, Inc. b 

Terrell, TX 

Large-Capacitv Group: d 


Gopher Smelting and Refining, Inc. 

Eagan, MN 

GNB, Inc. 

Vernon, CA 

RSR Corporation 

Indianapolis, IN 

Sanders Lead Company 

Troy, AL 

Schuylkill Metals Corporation 

Baton Rouge, LA 


Source: Reference 5. 


a Less than 22,000 tons. 

b These facilities were not operating as of January 1995. 
c 22,000 to 82,000 tons. 
d Greater than 82,000 tons. 


5-22 








5.3.2 Process Description 


The pyrometallurgical process used to extract copper from sulfide ore concentrates 
(“concentrates”) is based upon copper’s strong affinity for sulfur and its weak affinity for oxygen 
as compared to that of iron and other base metals in the ore. The purpose of smelting is to 
separate the copper from the iron, sulfur, and commercially worthless mineral materials generally 
referred to as “gangue.” All of the primary copper smelters currently produce anode copper from 
sulfur-bearing ores with the same basic processes: 10 

• matte smelting (i.e., smelting of concentrates to produce matte); 

• matte converting (to produce blister copper); and 

• refining of blister copper in an anode furnace (to produce anodes). 

Copper concentrates are received by the smelter that typically contain 24 to 30 percent copper, 

30 percent sulfur, 25 percent iron, and 10 to 20 percent oxides of silicon, calcium, aluminum, 
magnesium, and zinc (usually present as sulfide). (Copper-bearing ores typically contain 0.5 to 
1 percent copper by weight. A froth-flotation process is utilized to produce the “concentrate.” 
This froth-flotation process may or may not be performed at the smelter site.) Concentrates also 
contain impurities, such as lead, arsenic, antimony, cadmium, chromium, cobalt, manganese, 
mercury, nickel, and selenium. These impurities are typically found in combined concentrations 
of less than one percent. The smelter may also receive copper scrap (for direct input into the 
converters), or may receive other non-concentrate inputs, such as precipitates, or copper “speiss.” 

Incoming concentrates are typically dried before charging into a smelting furnace or 
reactor. Several types of smelting fumaces/reactors are currently utilized in the United States, 
including flash furnaces, CONTOP reactors, and IsaSmelt reactors. Figure 5-7 illustrates basic 
smelting operations. 10 


5-23 


Ore Concentrates with Silica Fluxes 


Slow Cool, 
Milling Flotation 



Anode Copper (>98.5% Cu) 
1 

To Electrolytic Refinery 

Figure 5-7. Typical Primary Copper Smelter Flow Sheet 


Source: References 10 and 11. 


5-24 









































The smelting fumace/reactor produces molten copper matte, typically containing 
55-75 percent copper, which is tapped from the furnace, and transferred by ladles to converters. 
The smelting fumace/reactors also produces slag, containing relatively low amounts of copper 
(typically less than two percent). This slag may be discarded directly, if less than 1 percent 
copper, or may be transferred to an electric slag cleaning vessel (for further copper removal), or 
may be cooled and reconcentrated (again, in an attempt for further copper removal). 

In the converters, further sulfur is removed from the matte, and in addition, iron is 
oxidized and separated by skimming. The output from the converters is “blister” copper, 
generally containing greater than 98 percent copper. Figure 5-8 illustrates a typical converter. 12 

Molten blister copper is poured from the converter, and transferred by ladles to anode 
furnaces, where further refining by removal of oxygen and other impurities takes place. The 
resulting “anode” copper is generally greater than 98.5 percent pure. It is cast into anodes for use 
in the final electrolytic refining step. 

Further refining of “anode” copper into “cathode” copper (greater than 99.9 percent 
purity) is performed by electrolytic means in a “tank house.” Production of cathode copper may 
or may not take place at the smelter site. 

5.3.3 Emissions 

PM and SCk are the principal air contaminants emitted from primary copper smelters. 
Actual emissions from a particular smelter will depend upon the smelting configuration (type and 
mix of equipment used), control devices applied, and the operating and maintenance practices 
employed. Typically, arsenic will be emitted as PM. In addition, actual arsenic emissions will 
vary depending on the quantity of arsenic introduced to the smelter as copper-bearing feed 
materials. Table 5-5 presents arsenic emission factors available from one EPA report. 13 In 


5-25 



Figure 5-8. Copper Converter 


Source: Reference 12. 


5-26 






TABLE 5-5. ARSENIC EMISSION FACTORS FOR PRIMAKY COPPER SMELTING FACILITIES 


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on 

i 

i 

m 

i 

m 

i 

CO 

i 

CO 

CO 

CO 

CO 

rn 

CO 

CO 

rn 

m 


c 

o 

o 

O 

O 

O 

O 

O 

O 

i 

O 

1 

o 

1 

o 

1 

o 

1 


1 

m 

1 

m 

t 

CO 

CO 

cn 

CO 

CO 

CO 

CO 

CO 

CO 

CO 

CO 


n 


5-27 


Emission factors are expressed in lb of pollutant emitted per ton of concentrated ore processed. To convert to kg per metric ton (kg/tonne), 
multiply by 0.5. 










addition to process emissions, significant quantities of fugitive emissions are also generated 
during material handling operations and furnace charging and.tapping. 

As a general observation, particulate emissions from primary smelting operations are 
predominantly metallic fumes in the submicrometer range. A variety of particulate contaminants 
are typically emitted during the roasting process. They vary in composition depending on the 
particular ore being roasted. Copper and iron oxides are the primary constituents, but other 
oxides such as those of arsenic, antimony, mercury, lead, cadmium, and zinc may also be present 
with metallic sulfates and sulfuric acid. Combustion products from fuel burning also contribute 
to the emissions from roasters and reverberatory smelting furnaces. 

Fugitive particulates emitted from primary copper smelting consist primarily of metallic 
oxides and dust. Major sources of fugitive emissions are shown in Figure 5-9. 10 Principal 
sources include ore concentrate unloading and handling, roaster calcine transfer operations, 
furnace tapping operations, and converter charging and skimming operations. 

5.3.4 Emission Control Techniques 

Control devices for particulate emissions from roasting, smelting, and converting 
operations include mechanical collectors (cyclones and settling flues), hot and cold ESPs, 
baghouses, and scrubbers. ESPs, usually preceded by mechanical collectors and operated at 
elevated temperatures, are by far the most common control devices. 

The control techniques applied vary depending on smelter configuration, process 
equipment mix, emissions characteristics, and feasibility for S0 2 control. Off-gases from 
smelting equipment that produce relatively high concentrations of S0 2 (greater than 4 percent; 
includes fluidized bed roasters, non-reverberatory smelting furnaces, and converters) are 
generally treated in single- or double-contact sulfuric acid plants for S0 2 removal. 


5-28 



d 


OJ 

u 

c 

u 


DC 


<u 

u 


3 

O 

c/i 


5-29 


Figure 5-9. Fugitive Emission Sources at Primary Copper Smelters 






































Fugitive emissions produced by the majority of smelter fugitive sources, including 
concentrate handling, dried concentrate transfer, and furnace tapping (matte and slag), are 
controlled by enclosing the fugitive emission points in a hood and exhausting the captured 
emissions to a control device for collection. Fugitive emissions associated with converter 
operations are much more difficult to control. These emissions are substantial and occur during 
charging, skimming, or pouring operations when the converter mouth is rotated out from under 
the primary hood. They also result from primary hood leakage. Control techniques for converter 
fugitive emissions include secondary hoods of various designs and ventilating the converter 
building to a control device. 3 

5.3.5 Source Location 

There are seven primary copper smelters in the United States. The names and locations 
of these seven smelters are listed in Table 5-6. 10 Three facilities are located in Arizona, two in 
New Mexico, and one each in Texas and Utah. 


TABLE 5-6. PRIMARY COPPER SMELTERS IN THE UNITED STATES 


Owner/Operator 

Location 

ASARCO, Incorporated 

ASARCO, Incorporated 

Cyprus Miami Mining Corporation 

Kennecott Utah Copper Corporation 

Broken Hill Propriety 

Phelps Dodge-Chino Mines Company 

Phelps Dodge Mining Company 

El Paso, Texas 

Hayden, Arizona 

Claypool, Arizona 

Magna, Utah 

San Manuel, Arizona 

Hurley, New Mexico 

Playas, New Mexico (Hidalgo County) 3 


Source: References 10 and 11. 

a Although the mailing address of the Phelps Dodge-Hidalgo smelter is Playas, New Mexico, the smelter is actually 
located in Hidalgo County, New Mexico. 


5-30 





5.4 Secondary Aluminum Operations 

5.4.1 Source Description 

Secondary aluminum operations involve the cleaning, melting, refining, alloying, and 
pouring of aluminum recovered from scrap, foundry returns, and dross. The processes used to 
convert scrap aluminum to secondary aluminum products such as lightweight metal alloy for 
industrial castings and ingots are presented in Figures 5-10 and 5-11. 14 Production involves two 
general classes of operations: scrap treatment and smelting/refining. 

5.4.2 Process Description 

Scrap treatment involves receiving, sorting, and processing scrap to remove contaminants 
and prepare the material for smelting. Processes based on mechanical, pyrometallurgical, and 
hydrometallurgical techniques are used, and those employed are selected to suit the type of scrap 

processed. 

The smelting/refining operation generally involves the following steps: (1) charging, 

(2) melting, (3) fluxing, (4) alloying, (5) mixing, (6) demagging, (7) degassing, (8) skimming, 
and (9) pouring. All of these steps may occur at each facility, with process distinctions being in 
the furnace type used and emissions characteristics. However, as with scrap treatment, not all of 
these steps are incorporated into the operations at a particular plant. Some steps may be 
combined or reordered, depending on furnace design, scrap quality, process inputs, and product 
specifications. 14 

Purchased aluminum scrap undergoes inspection upon delivery and is sorted into the 
categories shown in Figure 5-10. Clean scrap requiring no treatment is transported to storage or 
is charged directly into the smelting furnace. The bulk of the scrap, however, must be manually 
sorted as it passes along a steel belt conveyor. Free iron, stainless steel, zinc, brass, and oversize 


5-31 



PRETREATMENT 

A n 




iBULK SCRAP 


J 


INSPECTION 


NEW CLIPPINGS 
FORGINGS 


» CABLE 


SHREDDING/ 

CLASSIFYING 


FUEL¬ 


SORTING 



BORINGS. 




TURNINGS 



CRUSHING. | 
SCREENING’ 
H5CC 


BURNING. 
DRYING 

|5CC 3-04-001-09) 



HEAVY METALLIC 
SKIMS 


FUEL 


RESIDUES 


HOT DROSS 4-FLUX 

PROCESSING 

(SCC 3-04-001-07| 


-HDRY MILLING 

(SCC 3-04-001-16) 


LEACHING 

(SCC 3-04-001 -18) 


WATER 


* FOIL 


£ 


FUEL 


* ROASTING 



HIGH IRON 


SWEATING 



SCRAP 


(SCC 3-04-001-01) 

" ' 11 


FUEL 


Figure 5-10. Typical Process Diagram for Pretreatment in the Secondary Aluminum 

Processing Industry 


Source: Reference 14. 


5-32 

























































































PRODUCT 


r 


SMELTING/REFINING 




N Y 




Figure 5-11. Typical Process Flow Diagram for the Secondary Aluminum 

Processing Industry 


Source: Reference 14. 


5-33 
















































materials are removed. The sorted scrap then goes to appropriate scrap treating processes, if 
necessary, or is charged directly to the smelting furnace. The more common scrap treatment 
processes are discussed in the following paragraphs. 

Sorted scrap is conveyed to a ring crusher or hammer mill where the material is shredded 
and crushed, and the iron is tom away from the aluminum. The crushed material passes over 
vibrating screens to remove dirt and fines, and tramp iron is removed by magnetic drums and/or 
belt separators. Baling equipment compacts bulky aluminum scrap into bales. 

Pure aluminum cable with steel reinforcement or plastic insulation is cut by alligator-type 
shears and granulated or further reduced in hammer mills to separate the iron core and the plastic 
coating from the aluminum. Magnetic processing removes the iron and air classification 
separates the insulation. Borings and turnings, in most cases, are treated to remove cutting oils, 
greases, moisture, and free iron. The processing steps involved are (1) crushing, (2) drying to 
remove oil and moisture, (3) screening to remove aluminum fines, (4) removing iron 
magnetically, and (5) storing the clean dried borings in tote boxes. 14 

Several types of residue from primary and secondary aluminum plants contain 
recoverable amounts of aluminum. Aluminum is recovered from hot and cold drosses by batch 
fluxing in rotary furnaces. In the dry milling process, cold aluminum dross and other residues are 
processed by milling, screening, and concentrating to reduce oxides and non-metallic materials to 
fine powders, yielding a product which is 60 to 70 percent aluminum. 

Drosses, skimmings, and slags are treated by leaching to remove fluxing salts and other 
nonrecoverable materials. First, the raw material is fed into a long, rotating drum or an attrition 
or ball mill, from which soluble contaminants are leached. The washed material is then screened 
to remove fines and dissolved salts and is dried and passed through a magnetic separator to 
remove ferrous materials. The non-magnetic materials are then stored or charged directly to the 
smelting furnace. 


5-34 


Aluminum foil is treated by roasting to separate carbonaceous materials associated with 
the aluminum. 

Sweating is a pyrometallurgical process using open-flame reverberatory furnaces to 
recover aluminum from scrap with high iron content. The aluminum and other constituents with 
low-melting temperatures melt, trickle down the hearth, through a grate, and into molds or 
collecting pots. The materials with higher-melting temperatures, including iron, brass, and 
oxidation products formed during the sweating process, remain in the furnace until they are 
removed. Treated aluminum scrap is transferred to the smelting/refining operations for 
refinement into finished products. 

In smelting/refining operations, reverberatory furnaces are commonly used to convert 
clean, sorted scrap, sweated pigs, or untreated scrap to ingots, shot, or hot metal. The scrap is 
first mechanically charged to the furnace, often through charging wells designed to introduce 
chips and light scrap below the surface of a previously melted charge (“heel”). Batch processing 
is generally practiced for alloy ingot production, and continuous feeding and pouring are 
generally used for products having less strict specifications. 

Cover fluxes are used to prevent oxidation of the melt caused by air contact. Solvent 
fluxes react with non-metallic materials, such as burned coating residues and dirt, to form 
insoluble materials that float to the surface as part of the slag. Alloying agents are charged to the 
furnace in amounts determined by product specifications. Nitrogen or other inert gases can be 
injected into the molten metal to help raise dissolved gases (typically hydrogen) and intermixed 
solids to the surface. 

Demagging reduces the magnesium content of the molten charge from approximately 
0.3 to 0.5 percent (typical scrap value) to about 0.1 percent (typical product line alloy 
specification). When demagging with chlorine gas, chlorine is injected under pressure through 
carbon lances to react with magnesium and aluminum as it bubbles to the surface. Other 


5-35 


chlorinating agents or fluxes, such as anhydrous aluminum chloride or chlorinated organic 
compounds, are sometimes used. 

In the skimming step, contaminated semi-solid fluxes'(dross, slag, or skimmings) are 
ladled from the surface of the melt and removed through the forewell. The melt is then cooled 
before pouring. 

The reverberatory (fluorine) process is similar to the reverberatory (chlorine) 
smelting/refining process, except that aluminum fluoride (A1F 3 ) is employed in the demagging 
step instead of chlorine. The A1F 3 reacts with magnesium to produce molten metallic aluminum 
and solid magnesium fluoride salt, which floats to the surface of the molten aluminum and is 
skimmed off. . 

The crucible smelting/refining process is designed to produce harder aluminum alloys by 
blending pure aluminum and hardening agents in an electric induction furnace. The process steps 
include charging scrap to the furnace, melting, adding and blending the hardening agent, 
skimming, pouring, and casting into notched bars. 14 

5.4.3 Emissions and Control 

Each processing step in the secondary aluminum industry is a potential source of arsenic 
emissions, which are generally emitted as PM. Arsenic emissions will be a small fraction of total 
particulate emissions and will vary with the arsenic content of the scrap. Table 5-7 presents 

i 

arsenic emission factors for specific processing units. 15,16 

Data for arsenic emissions from secondary aluminum processing facilities were scarce. 
Currently, emissions data from secondary aluminum facilities are being collected for inclusion in 
the secondary aluminum MACT, which may augment the information provided here. 


5-36 


TABLE 5-7. ARSENIC EMISSION FACTORS EOR SECONDARY ALUMINUM PRODUCTION 



i> 





CJ 





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w-> 

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60 





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5-37 










There is potential for particulate emissions from several processing steps, including 
crushing/screening, shredding/classifying, baling, buming/drying, dross processing, roasting, 
smelting/refining, and demagging. Particulate emissions may also be released by leaching 
operations during drying. Fumes may be emitted from fluxing reactions. Arsenic emission 
levels from each of these processes depends on the arsenic content of the feed introduced to each 
unit step . 14 

Typical control devices at secondary aluminum operations include baghouses, 
multicyclones, scrubbers, and local ventilation. These have been designed primarily for PM 
control; but in controlling PM, gaseous arsenic emissions are controlled. 

5.5 Ferroalloy Production 

5.5.1 Source Description 

The term “ferroalloy” refers to an alloy of iron with some element other than carbon. 
Ferroalloys are typically used to impart distinctive qualities to steel and iron. Production of 
calcium carbide and silicon metal are also included in the ferrolloy source category (though they 
are not ferralloys) because they are manufactured using essentially the same equipment and 
processes. 

The ferroalloy industry is closely related to the iron and steel industries, its largest 
consumers. Ferroalloys provide unique qualities to steel and cast iron and serve important 
functions during iron and steel production cycles. The primary ferroalloys are those of 
chromium, manganese, and silicon. In addition, boron, cobalt, columbium, copper, 
molybdenum, nickel, phosphorus, titanium, tungsten, vanadium, zirconium, and the rare earths 
provide special characteristics and are often added as ferroalloys. 


5-38 


In 1989, the United States ferroalloy production was approximately 985,000 tons, 
significantly less than shipments in 1975 of approximately i',770,000 tons. There were 28 
companies that produced ferroalloys in 1989. 17 

5.5.2 Process Description 

Ferroalloys are typically produced with submerged electric arc furnaces; however, 
exothermic (metallothermic) reaction furnaces and electrolytic cells can also be used to produce 
ferroalloys. Table 5-8 presents furnace descriptions along with their ferroalloy products. A 
typical ferroalloy plant is illustrated in Figure 5-12. 17 

Submerged electric arc furnaces usually produce a desired product directly, however, they 
may also produce an intermediate product that is subsequently used in additional processing 
methods. The submerged arc process is a reduction process. The reactants are made up of 
metallic ores (ferrous oxides, silicon oxides, manganese oxides, chrome oxides, etc.) and a 
carbon-source reducing agent, typically in the form of coke, charcoal, high- and low-volatility 
coal, or wood chips. Sometimes limestone is added as a flux material. Before being conveyed to 
a mix house for blending and weighing, raw materials are crushed, sized, and in some instances, 
dried. The processed material is then transported by conveyers, buckets, skip hoists, or cars to 
hoppers above the furnace. The mix is then gravity-fed through a feed chute as needed 
(i.e., continuously or intermittently). At high temperatures in the reaction zone, the carbon 
source reacts with metal oxides to form carbon monoxide and to reduce the ores to base metal. A 
typical reaction yielding ferrosilicon is presented below: 

Fe 2 0 3 + 2SiC>2 + 7C - 2FeSi + 7 CO 

Smelting in an electric arc furnace is established by converting electrical energy to heat. 
As an alternating current is applied to the electrodes, current is forced to flow through the charge 
between the electrode tips. This produces a reaction zone at temperatures up to 3,632°F. The tip 


5-39 


TABLE 5-8. FERROALLOY PROCESSES AND RESPECTIVE PRODUCT GROUPS 


Process 

Product 

Submerged arc fumace a 

Silvery iron (15-22% Si) 

Ferrosilicon (50% Si) 

Ferrosilicon (65-75% Si) 

Silicon metal 

Silicon/manganese/zirconium (SMZ) 

High carbon (HC) ferromanganese 
Siliconmanganese 

HC ferrochrome 

Ferrochrome/silicon 

FeSi (90% Si) 

Exothermic b 


Silicon reduction 

Low carbon (LC) ferrochrome 

LC ferromanganese 

Medium carbon (MC) ferromanganese 

Aluminum reduction 

Chromium metal 

Ferrotitanium 

Ferrocolumbium 

Ferovanadium 

Mixed alurrunothermal/silicothermal 

Ferromolybdenum 

Ferrotungsten 

Electrolytic 0 

j 

Chromium metal 

Manganese metal 

Vacuum fumace d 

LC ferrochrome 

Induction furnace 0 

Ferrotitanium 


Source: Reference 17. 


Process by which metal is smelted in a refractory-lined cup-shaped steel shell by submerged graphite 
electrodes. 

b Process by which molten charge material is reduced, in exothermic reaction, by addition of silicon, aluminum, 
or a combination of the two. 

Process by which simple ions of a metal, usually chromium or manganese in an electrolyte, are plated on 
cathodes by direct low-voltage current. 

d Process by which carbon is removed from solid-state high-carbon ferrochrome within vacuum furnaces 
maintained at temperatures near melting point of alloy. 

Process that converts electrical energy into heat, without electrodes, to melt metal charges in a cup or drum- 
shaped vessel r 


5-40 







<u 

o 

c 

o 


o 

OS 


<D 

u 


o 


5-41 


Figure 5-12. Typical Ferroalloy Production Process 






































































of each electrode switches polarity continuously as the alternating current flows between the tips. 
A uniform electric load is maintained by continuously varying electrode depth by mechanical or 
hydraulic means. 

Figure 5-13 depicts the design of a typical covered submerged electric arc furnace. The 
lower portion of the furnace is comprised of a cylindrical steel shell with a flat bottom or hearth. 
The shell is sometimes water-cooled to protect it from the heat of the process. For covered or 
semi-covered furnaces (but not for open-design furnaces), a water-cooled cover and fume 
collection hood are installed over the furnace shell. Typically, three carbon electrodes extend 
through the cover and into the furnace shell opening. Raw materials can be charged to the 
furnace through feed chutes from above the furnace. The surface of the furnace charge, which 
contains both molten material and unconverted charge during operation, is normally kept near the 
top of the furnace shell. The lower portions of the electrodes are placed at about 3 to 5 feet under 
the charge surface. Three-phase electric current arcs from electrode to electrode traveling 
through the charge material. As the electric energy is converted to heat, the charge material melts 
and reacts to form the desired product. The carbonaceous material in the furnace charge reacts 
with oxygen in the metal oxides of the charge and reduces them to base metals. This reaction 
generates large quantities of carbon monoxide that exits upwards through the furnace charge. 

The molten metal and slag are tapped through one or more tap holes protruding through the 
furnace shell at the hearth level. While power is applied continuously, feed material may be 
charged intermittently or continuously. Tapping, whether intermittent or continuous, is based on 
production rate of the furnace. 17 

There are two basic types of submerged electric arc furnaces, open and covered. The 
majority of the submerged electric arc furnaces in the U.S. are open furnaces. The open type 
furnaces have a fume collection hood at least 3.3 feet above the top of the furnace shell. In some 
situations, adjustable panels or screens are used to reduce the open space between the furnace and 
hood. This is also done to improve emissions capture efficiency. Fabric filters and ESPs are 
often used to control emissions from open furnaces. 


5-42 


CARBON ELECTRODES 



Figure 5-13. Typical Submerged Arc Furnace Design 

Source: Reference 17. 


5-43 





















































































































































































Some covered furnaces have a water-cooled steel cover that fits closely to the furnace 
shell. The goal of covered furnaces is to limit air filtration into the furnace gases, thereby 
reducing combustion of the gas. In doing so, the volume of gas requiring collection and 
treatment is reduced. Holes in the cover allow for the charge and electrodes to pass through. 
Covered furnaces that partially close these hood openings with charge material are referred to as 
“mix sealed” or “semi-closed furnaces.” While these covered furnaces significantly reduce air 
infiltration, some combustion still occurs under the furnace cover. Covered furnaces equipped 
with mechanical seals around the electrodes and sealing compounds are referred to as “sealed” or 
“totally closed.” These types of furnaces have minimal, if any, air infiltration and undercover 
combustion. 

Removal of the molten alloy and slag that accumulate on the furnace hearth is done 
through a tap hole. Typically this process takes 20 to 30 minutes. The molten metal and slag 
pour from the tap hole into a carbon-lined trough, then into a carbon-lined runner that directs the 
metal and slag into a reaction ladle, ingot molds, or chills. 

After the large ferroalloy castings are allowed to cool and solidify, they may be broken 
with drop weights or hammers. Broken pieces are then crushed, screened (sized), and stored in 
bins until shipment. 

The exothermic (metallothermic) process uses an intermediate molten alloy which may 
come directly from a submerged electric arc furnace or from another type of heating apparatus. 
The process is typically used to produce high-grade alloys with low-carbon content. As silicon 
and aluminum react with oxygen in the molten-alloy, low- and medium-carbon content 
ferrochromium and ferromanganese are produced. Aluminum reduction is used to produce 
chromium, ferrotitanium, ferrovanadium, and ferrocolumbium. A mixed alumino/silico thermal 
process is used to produce ferromolybdenum and ferrotungsten. Typically, exothermic processes 
are performed in open vessels and may have similar emissions to the submerged arc process for 
short periods during reduction. 


5-44 


Electrolytic processes are used to manufacture high-purity manganese and chromium. 
Electrolysis of an electrolyte taken from manganese ore or manganese-bearing ferroalloy slag is 
used to produce manganese. The following steps complete the process: (1) roasting the ore to 
convert it to manganese oxide, (2) leaching the roasted ore with sulfuric acid to solubilize 
manganese, (3) neutralization and filtration to extract iron and aluminum 
hydroxides,(4) purifying the leach liquor by treatment with sulfide and filtration to remove 
metals, and (5) electrolysis. 

Electrolytic chromium is typically produced from high-carbon ferrochromium. Hydrogen 
gas is produced by dissolving the alloy in sulfuric acid. The leachate is treated with ammonium 
sulfate and conditioned to remove ferrous ammonium sulfate and produce a chrome-alum for 
feed to the electrolysis cells. 17 

5.5.3 Emissions and Controls 

Particulate is generated from several operations during ferroalloy production. These 
operations include raw material handling, smelting, tapping, and product handling. Organic 
emissions are emitted almost entirely from smelting operations. The furnaces where smelting is 
completed are the primary (almost exclusive) sources of potential particulate and organic 
emissions. The reader is referred to Section 12.5 of AP-42 for particulate and size specific 
paniculate emissions factors for submerged arc electric furnaces. 17 Table 5-9 presents arsenic 

1 R 

emission factors for semi-covered electric arc furnaces. 

Paniculate emissions in the form of fumes from electric arc furnaces make up the vast 
majority (94 percent) of the total particulate emissions from the ferroalloy industry. In addition, 
substantial quantities of carbon monoxide and organic materials are emitted from electric arc 
furnaces. Organic emissions are much higher from covered furnaces than from open furnaces. In 
addition, dust is generated from a variety of activities including raw material storage and 
handling, heavy vehicle traffic, crushing, sizing and drying. Rotary and other types of dryers are 


5-45 


TABLE 5-9. ARSENIC EMISSION FACTORS FOR ELECTRIC ARC FURNACES 


CJ 

c-S 

O re 
’55 Om 

M 


UJ 


V 

OB 


oc „ 

«- x: 

2 £ 

3 5 

u. ^ 

= £ 

.2 c 

CO 

CO 


UJ 


CJ 

re 

U. 

•2 > 

C/D 

c/d 

ll 

aj c 

OB — 
re 

Ua 

> 

< 


(U 

CJ 

’> 

i) 

a 


c 

c 

U 


o 

i— 

3 

O 

OO 

c 

_o 

co 

CO 

£ 

u 


u 

u 

00 


D D D 


< < < 
Z Z Z 


rs 

O 


ro 

O O 


X 

O 

05 


X 

o 

m 


c-j — — 


aj 

aj 

3 

3 

O 

C 

Z 

z 


£ 

xi 

E 

$ 


3 

a 

<u 

> 


aj 

cj 

re 

3 


CJ 

i— 

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o 


cj 

a/ 


4J 

CJ 

re 

3 

L. 

3 

U. 

u 


< < 

CJ CJ 


CJ 

£ 

E 

3 

U- 


o 

aj 


U U U1 


o 

I 

r~ 


(N 

o 


<N 

o 



ro 

ro 

O 

O 

O 

ro 

rn 

fA 


00 


a> 

o 

c 

aj 

L. 

£ 

OJ 

CC 


v 

CJ 

ba 

3 

o 

00 


m 

Tt 

o 

►> 

JD 

>* 

•a 

i 


CB 


c 

aj 

> 

C 

o 

CJ 

aj 

£ 

E 

a 

X) 

T3 

aj 

E 

3 

co 

s 

o 

CJ 

OB 

b* 

aj 

c 

aj 


8 . 

•T3 

aj 


E 

aj 

s 

re 


.a> 


5-46 









often used to dry raw materials. These dryers can generate substantial quantities of particulate 
emissions. 

The majority of open electric arc furnaces are controlled with fabric filters, although to a 
much lesser extent, scrubbers and electrostatic precipitators are also used. 

For covered furnaces, two emission capture systems are necessary. While a primary 
capture system is used to withdraw gases from under the furnace cover, a secondary system 
captures fumes released around the electrode seals during tapping. Scrubbers are the most 
common control device used to control exhaust gases from sealed furnaces. Afterburners are 
always used to bum off CO after control devices for covered furnaces. 

Tapping operations also generate fumes. Some plants capture these emissions with a 
main canopy hood, while others use separate tapping hoods ducted to either the furnace 
emissions control device or a separate control device. 

Dust from pretreatment activities may be controlled by dust collection equipment such as 
scrubbers, cyclones, or fabric filters. 

5.6 Iron and Steel Foundries 

5.6.1 Process Description 

Iron and steel foundries produce gray, white, ductile, or malleable iron and steel castings. 
Both cast irons and steels are solid solutions of iron, carbon, and various alloying materials. 
Although there are many types of iron and steel, groups can be distinguished by their carbon 
composition. Cast iron typically contains 1 percent carbon or greater; cast steel usually contains 
less than 1 percent carbon. 18,19 


5-47 


Iron castings are used in many types of equipment, including motor vehicles, farm 
machinery, construction machinery, petroleum industry equipment, electrical motors, and iron 
and steel industry equipment. 

Steel castings are used in railroad equipment, construction machinery, motor vehicles, 
aircraft, agricultural equipment, ore refining machinery, and chemical manufacturing 
equipment. 18 Steel castings are classified on the basis of their composition and heat treatment, 
which is determined by their end use. Classifications include carbon, low-alloy, heat-resistant, 
corrosion-resistant, and wear-resistant. 

The following four basic operations are performed in all iron and steel foundries: 

• Storage and handling of raw materials; 

• Preparation of the molds to shape the molten metal; 

• Melting of the raw materials; and 

• Pouring of hot molten metal into molds. 

Other processes present in most foundries include: 

• Sand preparation and handling; 

• Mold cooling and shakeout; 

• Casting cleaning, heat treating, and finishing; 

• Coremaking; 

• Pattern making; and 

• Sand reclamation. 

A generic process flow diagram for iron and steel foundries is shown in Figure 5-14. 18 
Figure 5-15 depicts the emission points in a typical iron foundry. 17 


5-48 




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5-49 


Source: References 18 and 20. 

































Fugitive 

Particulates 



Figure 5-15. Emission Points in a Typical Iron and Steel Foundry 


Source: References 17 and 20. 


5-50 














































Metal Melting Process 


In a typical foundry operation, charges to the melting unit are sorted by size and density 

and cleaned (as required) prior to being put into the melter. Charges consist of scrap metal, 

% * 

ingot, carbon (coke), and flux. Prepared charge materials are weighed and transferred into the 
melting furnace by crane buckets, skip hoists, or belt feeders. The charge in an electric furnace 
or cupola is heated until it reaches a certain temperature and the desired product chemistry of the 
melt has been attained. After the desired product is obtained, the molten metal is either poured 
out of the furnace into various-size transfer ladles and then into the molds or it is transferred to 
holding furnaces for later use. 

The metal melting process in iron and steel foundries is accomplished in cupolas and in 
electric arc furnaces (EAFs) and electric induction furnaces (EIFs). Cupolas are used to melt iron 
for casting and are charged with alternate layers of coke, metallics, and fluxes. Combustion air 
is introduced into the cupola through tuyeres located at the base. The heat produced by the 
burning coke melts the iron, which flows down and is tapped from the bottom of the cupola. 
Fluxes combine with impurities in the charge and form slag, which is removed through tap holes 
located above the level of the metal tap hole. Cupola capacities range primarily from 1 to 30 tons 
per hour, with a few large units capable of producing close to 100 tons per hour. Larger furnaces 
are operated continuously for several days with inspections and cleanings between operating 
cvcles. 21 

j 

Iron and steel castings are produced in a foundry by pouring molten metal into molds 
made of sand, metal, or ceramic material. Steel foundries rely on EAFs or induction furnaces for 
melting purposes. In all types of foundries, when the metal has solidified, the molds are 
destroyed and the castings are removed on a shakeout unit. Abrasive (shotblasting) cleaning, 
grinding, and heat treating are performed as necessary. The castings are then inspected and 
shipped to plants of other industries for machining and assembly into a final product. 18 


5-51 


Mold and Core Production 


In addition to melting, the casting or mold pouring and cooling operations in iron and 
steel foundries are suspected to be a source of arsenic emissions. Also, mold preparation and 
casting shakeout (removal from the mold) activities are also suspect as arsenic emission sources, 
although test data are not available to quantify actual arsenic emissions. 

5.6.2 Emission Control Techniques 

Control technologies commonly used to control arsenic emissions from iron and steel 
foundry metal melting operations include baghouses and wet scrubbers. Fugitive emissions from 
molding, casting, and shakeout are generally controlled with local hooding or building ventilation 
systems that are ducted to a control device (predominantly baghouses). 21 

5.6.3 Emission Factors 

Arsenic emission factors were available for an arc furnace in a steel mill and cupola 
within an iron foundry. These emission factors are presented in Table 5-10. 22,23 

5.6.4 Source Locations 

There were 756 iron and steel foundries in the United States in 1992 based on a survey 
conducted by the EPA in support of the iron and steel foundry Maximum Achievable Control 
Technology (MACT) standard development. 24 In general, foundries are located in areas of heavy 
industry and manufacturing, especially areas where iron and steel are produced (e.g., the Great 
Lakes States). 


5-52 


TABLE 5-10. ARSENIC EMISSION FACTORS FOR IRON AND STEEL FOUNDRIES 


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5-53 










References For Section 5.0 


1. Woodbury, W.D. Annual Report 1990, Lead. Washington, D.C.: Bureau of Mines, 

U.S. Department of the Interior, U.S. Government Printing Office, April 1992. 

2. U.S. EPA. Compilation of Air Pollutant Emission Factors , 5th ed. (AP-42), Vol. I: 
Stationary Point and Area Sources, Section 12.6: Primary Lead Smelting. Research 
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air 
Quality Planning and Standards, 1995. 

3. U.S. EPA. Control Techniques for Lead Air Emissions, Unpublished Draft. Research 
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air 
Quality Planning and Standards, Emission Standards Division, 1990. 

4. U.S. EPA. Preliminary Study of Sources of Inorganic Arsenic. EPA-450/5-82-005. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office 
of Air Quality Planning and Standards, August 1982. 

5. U.S. EPA. Secondary Lead Smelting Background Information Document for Proposed 
Standards, V olume 1. EPA-450/R-94-024a. Research Triangle Park, North Carolina: 
U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, 
June 1994. pp. 2-1 to 2-36. 

6. Hall, R.M. and J.L. Gittleman. Control Technology for Metal Reclamation Industries at 
Sanders Lead Company Inc. CT-202-1 la. Cincinnati, Ohio: U.S. Department of Health 
and Human Services, Engineering Control Technology Branch, Division of Physical 
Sciences and Engineering, NIOSH, July 1993. pp. 1-8. 

7. Rives, G.D. and A.J. Miles, Radian Corporation. “Control of Arsenic Emissions from the 
Secondary Lead Smelting Industry - Technical Document.” Prepared for 

U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, 1985. 

8. Pacific Environmental Services, Inc. Draft Final Test Report, East Penn Manufacturing 
Company, Secondary Lead Smelter , Volume I, Report and Appendices A and B. 

Research Triangle Park, North Carolina: Pacific Environmental Services, Inc, 

March 15, 1994. 

9. U.S. EPA. Assessment of the Controllability of Condensible Emissions. 
EPA-600/8-90-075. Research Triangle Park, North Carolina: U.S. Environmental 
Protection Agency, Air and Energy Engineering Research Laboratory, October 1990. 

10. U.S. EPA. Primary Copper Smelters. National Emission Standards for Hazardous Air 
Pollutants (NESHAP), Final Summary Report. ESD Project No. 91/61. Research 


5-54 


Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air 
Quality Planning and Standards, Emission Standards Division, July 1995. 

11. Parameswaran, K. Asarcolnc. New York, NY. Fax to Phil Marsosudiro. Eastern 
Research Group. November 26, 1997 

12. U.S. EPA. Control Techniques for Lead Air Emissions, Vol. II, Chapter 4 to 
Appendix B. EPA-450/2-77-012. Research Triangle Park, North Carolina: 

U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, 
Emission Standards Division, 1977. 

13. U.S. EPA. Inorganic Arsenic Emissions from High-Arsenic Primary Copper Smelters 
Background Information for Proposed Standards. EPA-450/3-83-009a. Research 
Triangle Park, North Carolina: U.S. Environmental Protection Agency, April 1983. 

14. AP-42, 5th ed., op. cit., note 2. Section 12.8: Secondary Aluminum Operations, 1995. 
pp. 12.8-1 to 12.8-7. 

15. California Air Resources Board. Source Emissions Testing of an Aluminum Shredding 
and Delacquering System, March and April 1992. Confidential Report No. ERC-8. . 

16. California Air Resources Board. Emissions Measurements of a Delacquering Unit for 
AB2588 Toxics , September 7, 1991. Confidential Report No. ERC-32. 

17. AP-42, 5th ed., op. cit., note 2. Section 12.5: Iron and Steel Production, 1995. 

18. AP-42, 5th ed., op. cit., note 2. Section 12.5: Iron and Steel Production, 1995. 

19. Monroe, R. W. Steel Founders’ Society of America. Des Plaines, flinois. Letter to 

Dennis Beauregard. U.S. EPA, Research Triangle Park, North Carolina. 

September 30, 1997. 

20. Maysilles, J. U.S. Environmental Protection Agency. Memorandum to Dennis 
Beauregard. U.S. EPA, Research Triangle Park, North Carolina. September 1996 

21. U.S. EPA. Emission Factors for Iron Foundries - Criteria and Toxic Pollutants. EPA 
600/2-90-044. Cincinnati, Ohio: Control Technology Center, Office of Research and 
Development, 1990. 

22. California Air Resources Board. Source Emissions Testing from an ARC Furnace 
Baghouse. Confidential Report No. ERC-60. June 25, 1990. 


5-55 


23. California Air Resources Board. Source Emissions Testing of a Baghouse to Quantify 
Foundry Emissions. Confidential Report No. ERC-59. December 1990. 

24. California Air Resources Board. Source Emissions Testing of a Baghouse to Quantify 
Foundry Emissions. Confidential Report No. ERC-59. December 1990. 


5-56 


SECTION 6.0 


EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM 
THE PULP AND PAPER INDUSTRY 

Chemical wood pulping involves the extraction of cellulose from wood by dissolving the 
lignin that binds the cellulose fibers. Kraft pulping is the majorform of chemical wood pulping 
in the United States, accounting for approximately 85 percent of pulp production, 1 and is 
expected to continue as the dominant pulping process. 2,3 Semi-chemical and acid sulfite pulping 
constitute 6 and 4 percent of domestic pulp production, respectively. 1 

Four processes associated with the pulp and paper industry have been identified as 
potential sources of arsenic emissions: chemical recovery furnaces, smelt dissolving tanks, lime 
kilns, and power boilers. The following sections focus on the pulp mill thermal chemical 
recovery processes associated with potential arsenic emissions. Arsenic emissions from wood 
waste and fossil fuel-fired industrial power boilers are not specific to the pulp and paper industry 
and are discussed in Sections 4.1.1 and 4.1.2. 

6.1 Kraft Recovery Furnaces And Smelt-Dissolving Tanks 

6.1.1 Process Description 

The kraft pulping process involves the cooking or digesting of wood chips at an elevated 
temperature (340 to 360°F) and pressure (100 to 135 psig) in white liquor, which is a water 
solution of sodium sulfide (Na^S) and sodium hydroxide (NaOH). The lignin that binds the 
cellulose fibers is chemically dissolved by the white liquor in a tall, vertical digester. This 
process breaks the wood into soluble lignin and alkali-soluble hemicellulose and insoluble 
cellulose or pulp. A typical kraft pulping and recovery process is shown in Figure 6-1. 4 


6-1 



NONCONDENSABLES 


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Two types of digester systems are used in chemical pulping: batch and continuous. In a 
batch digester, the contents of the digester are transferred to’an atmospheric tank (usually referred 
to as a blow tank) after cooking is completed (2 to 6 hours). In a continuous digester, wood chips 
and white liquor continuously enter the system from the top while pulp is continuously 
withdrawn from the bottom into a blow tank. In both types of digesters, the entire contents of the 
blow tank are diluted and pumped to a series of brownstock washers, where the spent cooking 
liquor is separated from the pulp. The pulp, which may then be bleached, is pressed and dried 
into the finished product. 

The balance of the kraft process is designed to recover the cooking chemicals and heat. 
The diluted spent cooking liquor, or weak black liquor, which is 12 to 18 percent dissolved 
solids, is extracted from the brownstock washers and concentrated in a multiple-effect evaporator 
system to about 55-percent solids. The liquor is then further concentrated to 65-percent solids 
(strong black liquor) in a direct contact evaporator (DCE) or a nondirect contact evaporator 
(NDCE), depending on the configuration of the recovery furnace in which the liquor is 
combusted. DCE and NDCE recovery furnace schematics are shown in Figures 6-2 and 6-3, 
respectively. 5 

In older recovery furnaces, the furnace’s hot combustion gases concentrate the black 
liquor in a DCE prior to combustion. NDCEs include most furnaces built since the early 1970s 
and modified older furnaces that have incorporated recovery systems that eliminate conventional 
DCEs. These NDCEs use a concentrator rather than a DCE to concentrate the black liquor prior 
to combustion. In another type of NDCE system, the multiple-effect evaporator system is 
extended to replace the direct contact system. 

The strong black liquor is sprayed into a recovery furnace with air control to create both 
reducing and oxidizing zones within the furnace chamber. The combustion of the organics 
dissolved in the black liquor provides heat for generating process steam and, more importantly, 
for reducing sodium sulfate (Na^C^) to Na^ to be reused in the cooking process. Na^C^, 
which constitutes the bulk of the particulates in the furnace flue gas, is recovered and recycled by 
an ESP. After combustion, most of the inorganic chemicals present in the black liquor collect as 


6-3 



6-4 


Figure 6-2. Direct Contact Evaporator Recovery Boiler 



























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a molten smelt (containing sodium carbonate [Ns^COj] and Na^) at the bottom of the furnace, 
where they are continuously withdrawn into a smelt-dissolving tank. Molten smelt in the 
smelt-dissolving tank is contacted with mill water or weak wash (the filtrate from lime mud 
washing) to form green liquor. • . 

In addition to straight kraft process liquor, semi-chemical pulping process spent liquor, 
known as brown liquor, may also be recovered in kraft recovery furnaces. The semi-chemical 
pulping process is a combination of chemical and mechanical pulping processes that was 
developed to produce high-yield chemical pulps. In the semi-chemical process, wood chips are 
partially digested with cooking chemicals to weaken the bonds between the lignin and the wood. 
Oversize particles are removed from the softened wood chips and the chips are mechanically 
reduced to pulp by grinding them in a refiner. The most common type of semi-chemical pulping 
is referred to as neutral sulfite semi-chemical (NSSC). A major difference between the 
semi-chemical process and the kraft/sulfite pulping process is that the semi-chemical digestion 
process is shorter and wood chips are only partially delignified. Some semi-chemical pulp mills 
are, as of 1997, using chemical recovery. 6 Also, as mentioned above, some mills combine spent 
liquor from on-site semi-chemical process with spent liquor from adjacent kraft process for 
chemical recovery. 1 

Particulate emissions from the kraft recovery furnaces consist primarily of Na 2 S0 4 and 
Na 2 C0 3 , with some sodium chloride. Particulate emissions also contain arsenic, but only in 
minute quantities because arsenic is found as a contaminant in process chemicals and in trace 
amounts in wood. Particulate control and, therefore, arsenic control on recovery furnaces is 
achieved with ESPs, including both wet- and dry-bottom and, to a lesser extent, with scrubbers. 
Further particulate control is necessary for DCEs equipped with either a cyclonic scrubber or a 
cascade evaporator because these devices are generally only 20- to 50-percent efficient for 
particulates. 4 Most often in these cases, an ESP is employed after the DCE for an overall 
particulate control efficiency range of 85 percent to more than 99 percent. At existing mills, 
auxiliary scrubbers may be added to supplement older and less efficient primary particulate 
control devices. No specific data were available in the literature documenting lead control 
efficiencies for ESPs and scrubbers on kraft black liquor recovery furnaces. 


6-6 


6.1.2 Emission Factors 


Emission factors for arsenic from kraft recovery furnaces were developed from data 
provided by the National Council for Air and Stream Improvement (NCASI), an industry 
environmental research organization. 7,8 Kraft fumace/control configurations represented 
included a DCE recovery furnace equipped with an ESP and scrubber in series, a DCE recovery 
furnace equipped with only an ESP, an NDCE recovery furnace equipped with an ESP and 
scrubber in series, and an NDCE recovery furnace equipped with only an ESP. Emissions data 
were also provided for smelt-dissolving tanks (3). Arsenic emission factors for kraft black liquor 
recovery furnaces and smelt-dissolving tanks are presented in Table 6-1. 

6.1.3 Source Locations 

The distribution of kraft pulp mills in the United States in 1997 is shown in Table 6-2. 6 
Kraft pulp mills are located primarily in the southeast, whose forests provide over 60 percent of 
U.S. pulpwood. 1 

6.2 Lime Kilns 

6.2.1 Process Description 

In the kraft process, green liquor from the smelt-dissolving tanks is clarified and reacted 
with burnt lime (CaO) in a lime slaker. Following a series of causticizing vessels, the resultant 
white liquor is clarified to yield Na^ + NaOH (aqueous white liquor) and lime mud or calcium 
carbonate (CaC0 3 ). The white liquor is recycled to the digestion process and the lime mud is 
calcined in a lime kiln to regenerate CaO. 5 

A lime kiln is a countercurrent, inclined tube process heater designed to convert lime mud 
(CaC0 3 ) to CaO for reuse in the causticizing of kraft liquor. A process flow diagram for a lime 
kiln is shown in Figure 6-4. The rotary kiln is the most common lime kiln design used in the 
kraft pulp and paper industry. Rotary lime kilns range from 8 to 13 feet in diameter, and from 


6-7 


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TABLE 6-2. DISTRIBUTION OF KRAFT PULP MILLS IN THE UNITED STATES (1997) 


State 

Number of Mills 

Alabama 

14 

Arizona 

1 

Arkansas 

7 

California 

2 

Florida 

7 

Georgia 

12 

Idaho 

1 

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2 

Louisiana 

10 

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7 

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6 

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6 

Ohio 

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1 

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7 

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3 

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6 

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2 

Texas 

6 

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4 

Washington 

6 

Wisconsin 

4 

Total 

124 


Source: Reference 6. 


6-9 







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100 to 400 feet in length. Lime kilns predominantly fire natural gas, with some units firing 
distillate and/or residual fuel oil. Many facilities incinerate non-condensible gases (NCG) from 
pulping source vents in lime kilns to control total reduced sulfur (TRS) emissions. Temperatures 
in the kiln can range from 300 to 500 °F at the upper or wet end to 2,200 to 2,400 °F at the hottest 
part of the calcination zone near the lower or dry end. 5,9 

Emissions of concern from lime kilns include PM, largely in the form of calcium salts. 
Some of the PM also contains arsenic. Emissions of arsenic from lime kilns are likely due to the 
arsenic content of the lime mud with some contribution from the combustion of fossil fuel 
(natural gas or fuel oil). The most common PM control technologies used on lime kilns are 
scrubbers (some ESPs are also used). Scrubbers on lime kilns use either fresh water or clean 
condensates from pulping sources as a scrubbing medium. Small amounts of caustic solution 
may be added to the scrubbing solution to scrub TRS & S0 2 . Lime kiln scrubber designs include 
impingement, venturi, and cyclonic scrubbers. 10 

6.2.2 Emission Factors 

Arsenic emission factors for uncontrolled and scrubber-controlled lime kilns are 
presented in Table 6-3. 6,7,11 

6.2.3 Source Locations 

Lime kilns are primarily located at kraft process pulp mills. See Table 6-2 in Section 6.1 
for kraft pulp mill source locations reported in 1997. 

6.3 Sulfite Recovery Furnaces 

6.3.1 Process Description 

Although not as commonplace, the acid sulfite pulp production process is similar to the 
kraft process except that different chemicals are used for cooking. Sulfurous acid is used in place 


6-11 


TABLE 6-3. ARSENIC EMISSION FACTORS FOR LIME KILNS 


see 


Control 

Average Emission Factor 

Emission 


Number 

Emission Source 

Device 

in lb/MMton BLS a 

Factor Rating 

Reference 

3-07-001-06 

Lime Kiln 

None 

4.68x1 O' 7 b . 

U 

11 



Scrubber 

14.5 

D 

7,8 


a Emission factors in lb per million ton of black liquor solids generated of the mill. To convert to kg per million 
metric tons (kg/MMtonne), multiply by 0.5. 
b Emission factors in lb per air dry ton of pulp produced. 

of a caustic solution to dissolve wood lignin. To buffer the cooking solution, a bisulfite of 
sodium, magnesium, calcium, or ammonium is used. Digestion occurs under high temperature 
and pressure, as in the kraft process, in either batch mode or continuous digesters. Following 
digestion and discharge of the pulp into an atmospheric blow pit or dump tank, the spent sulfite 
liquor, known as red liquor, may be treated and discarded, incinerated, or sent through a recovery 
process for recovery of heat and chemicals. Additionally, chemicals can be recovered from 
gaseous streams such as those from red stock washers. The cost of the soluble bases, with the 
exception of calcium, makes chemical recovery economically feasible. 1,5 A simplified process 
schematic of magnesium-based sulfite pulping and chemical recovery is shown in Figure 6-5. 

Chemical recovery in the sulfite process involves the concentration of weak red liquor in 
multiple effect evaporators and DCEs to strong red liquor (55 to 60 percent solids). This liquor 
is sprayed into a furnace and burned, producing steam for mill processes. When 
magnesium-based liquor is burned, magnesium oxide is recovered from the flue gas in a 
multicyclone. The collected magnesium oxide is then water-slaked and used as circulation liquor 
in a series of venturi scrubbers designed to absorb S0 2 from the flue gas to form bisulfite 
solution for use in the cook cycle. 

Several processes for chemical recovery from sodium-base liquor are based upon the 
combustion of concentrated liquor in a kraft-type recovery furnace. The resultant smelt is similar 
in composition to that produced by combustion of kraft liquor. The commercial approaches to 
convert sodium-base smelt chemicals into regenerated cooking liquor include Sivola-Lurgi, 


6-12 









Potential POM 
Emissions 
Recovery Furnace/ 
Absorption Stream 
Exhaust 



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6-13 


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Figure 6-5. Process Diagram for Magnesium-Based Sulfite Pulping and Chemical Recovery 






































































































Tampella, Storm, Mead, and Rayonier. 12 Sulfite mills that do not practice chemical recovery 
require an acid plant to fulfill total sulfite demand. This is accomplished by rotary or spray sulfur 
burners equipped with heat exchangers and S0 2 -absorbing scrubbers. 

6.3.2 Emission Factors 

As with the kraft process, arsenic exists only as a contaminant in process chemicals and 
in trace amounts in wood, and is, therefore, released in minute quantities. Only one emission 
factor was available in the literature for arsenic from an uncontrolled sulfite recovery furnace. 

The arsenic emission factor is presented in Table 6-4. 7,8 

6.3.3 Source Locations 

Sulfite recovery furnaces are located at sulfite process pulp mills. Table 6-5 shows the 
distribution of sulfite pulp mills in the United States in 1997. 1 


6-14 


TABLE 6-4. ARSENIC EMISSION FACTORS FOR SULFITE PROCESS 

RECOVERY FURNACES 


SCC Number 

Emission Source 

Control 

Device 

Average Emission 
Factor in lb/MMton 
RLS a 

Emission 
Factor Rating 

3-07-002-22 

Sulfite Recovery 
Furnace 

None 

3.4 

D 


Source: References 7 and 8. 

Emission factors in lb pollutant per million ton of red liquor solid burned. To convert to kg per million metric tons 
(kg/MMtonne) multiply by 0.5. 


TABLE 6-5. DISTRIBUTION OF SULFITE PULP MILLS IN THE UNITED 

STATES (1997) 


State Number of Mills 


Alaska 1 

Florida 1 

Maine 1 

New York 1 

Pennsylvania 1 

Washington 5 

Wisconsin 4 

Total • 14 


Source: Reference 6. 


6-15 














References for Section 6.0 


1. U.S. EPA. Pulp, Paper, and Paperboard Industry-Background Information for 
Proposed Air Emission Standards: Manufacturing Processes at Kraft, Sulfite, Soda, and 
Semi-Chemical Mills. EPA-453/R-93-050a. Research Triangle Park, North Carolina: 
U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, 
Emission Standards Division, October 1993. pp. 2-1 to 2-22. 

2. Air and Waste Management Association. Air Pollution Engineering Manual. 

Chapter 18: Wood Processing Industry. New York, New York: Van Nostrand Reinhold, 
1992. 

3. Dyer, H., S. Gajita, and M. Fennessey. 1992 Lockwood-Post’s Directory of the Pulp, 
Paper and Allied Trades. San Francisco, California: Miller Freeman Publications, 1991. 

4. U.S. EPA. Compilation of Air Pollutant Emission Factors , 5th ed. (AP-42), Vol. I: 
Stationary Point and Area Sources, Section 10.2: Chemical Wood Pulping. Research 
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air 
Quality Planning and Standards, 1995. 

5. Radian Corporation. Pulp and Paper Industry Training Session Notes. Research Triangle 
Park, North Carolina: Radian Corporation, 1993. 

6. Dyer, H., S. Gajita, and M. Fennessey. 1997 Lockwood-Post's Directory of the Pulp, 
Paper and Allied Trades. San Francisco, California: Miller Freeman Publications, 1997. 

7. Someshwar, A. (NCASI, Gainesville, Florida). Memorandum to Dennis Beauregard 
(U.S. Environmental Protection Agency, Research Triangle Park, North Carolina) 
concerning air toxics emissions data for sources at chemical wood pulp mills. 

March 15, 1996. 

8. Someshwar, A. (NCASI, Gainesville, Florida). Memorandum to Jack Johnson (Radian 
International, LLC, Research Triangle Park, North Carolina) concerning emissions data 
for sources at chemical wood pulp mills. May 15, 1996. 

9. U.S. EPA. Environmental Pollution Control-Pulp and Paper Industry, Part 1: Air. 
EPA-625/7-76-001. Research Triangle Park, North Carolina: U.S. Environmental 
Protection Agency, Emission Standards Division, October 1976. pp. 11-1 to 11.11. 

10. NCASI. Compilation of Air Toxic Emission Data for Boilers, Pulp Mills, and Bleach 
Plants, Technical Bulletin No. 650. New York, New York: National Council of the 
Paper Industry for Air and Stream Improvement, June 1993. 

11. ECOSERVE. Pooled Air Toxics Source Test Program for Kraft Pulp Mills, Report 
No. 2, Simpson Paper Company, Anderson, California. Report No. 1249A. 

ECOSERVE, Inc., Environmental Services, November 27, 1990. 


6-16 


12. Smook, G.A. Handbook for Pulp and Paper Technologists. Atlanta, Georgia: TAPPI, 
1989. pp. 148-150. 


6-17 


















. 
























■ 




. 






' 







































■ 










' 






■ 










































SECTION 7.0 

EMISSIONS OF ARSENIC AND ARSENIC COMPOUNDS FROM OTHER SOURCES 


This section provides an overview of the miscellaneous sources of arsenic emissions. 
These sources can be divided into the following categories: Glass Manufacturing; Municipal 
Solid Waste Landfills; Asphalt Concrete Production; Abrasive Grain Processing; Prepared Feeds 
Manufacturing; Portland Cement Production; Open Burning of Scrap Tires; Grain Milling; 
Process Heaters; and Cotton Production and Ginning. Section 7.0 accounts for the smaller 
producers of arsenic emissions. Processes and associated emissions are provided, where known. 
Often, these sources are incomplete, therefore the reader should contact sources of interest to 
verify the process and control techniques employed prior to applying any emission factor 
presented in this section. 

The reader should also note that TRI data indicate that arsenic is potentially emitted from 
facilities within the categories listed in Table 7-1; 1 however, specific emissions data are lacking 
and current literature does not indicate the origins of these emissions. Therefore, further 
discussion of these sources is not included in this section. 

7.1 Glass Manufacturing 

Commercially produced glass is classified as soda-lime, lead, fused silica, borosilicate, or 
96 percent silica. Four basic operations are performed in all glass manufacturing facilities: 

(1) preparation of raw material, (2) melting in a furnace, (3) forming, and (4) finishing. 2 

The products of the industry are flat glass (SIC 3211), container glass (SIC 3221), pressed 
and blown glass (SIC 3229) and wool fiberglass (SIC 3296). The operations for glass 


7-1 


TABLE 7-1. OTHER SOURCES OF ARSENIC EMISSIONS 


Source Category 

Number of Sources Reported in 
TRI 

Pharmaceutical preparations manufacturing 

2 

Electrometallurgical products manufacturing 

1 

Storage batteries manufacturing 

2 

Sawmills and planing mills, general 

2 

Petroleum refining 

2 

Small arms munitions manufacturing 

2 

Plating and polishing 

1 

Nonferrous rolling and drawing 

1 

Medicinals and botanicals manufacturing 

1 

Copper rolling and drawing 

1 

Other biological incineration 

1,700 


Source: Reference 1. 

manufacturing are generally the same for all products except for forming, finishing and post 
processing. 3 

7.1.1 Process Description 

Raw materials including silica sand, limestone, soda ash and minor ingredients are 
received and stored at a production facility called a batch plant. The raw materials are then 
transferred to a weigher and mixed for a set period of time. Cullet (recycled glass) is added to 
assist in the melting process. The mixture (batch) is conveyed to a batch storage bin where it is 
held until fed into the melting furnace on a demand basis. 3 

Next, these raw materials are melted in a glass melting furnace to form a homogenous 
liquid at approximately 2,800°F. The continuous furnaces are charged continuously or 
intermittently by means of automatic or manual feeders. The glass furnaces are generally of the 
regenerative or recuperative type fired by gas or oil with electric boosting for additional heating 


7-2 





and control. Production of certain low viscosity glasses such as crystal which require special 
production techniques may be carried out in day tanks. The melted glass is held at the molten 
state until it reaches a desired red state of homogeneity and is then cooled to about 2,200 °F or 
less for delivery to the forming stage of the process. 3 

Finally, the molten material is drawn from the furnace and worked on forming machines 
by a variety of methods, including pressing, blowing, drawing, or rolling to produce the desired 
product. 

The end product undergoes finishing (decorating or coating) and annealing (removing 
unwanted stress areas in the glass). Any damaged or undesirable glass is transferred back to the 
batch plant to be used as cullet. 

7.1.2 Emission Control Techniques 

Baghouses, venturi scrubbers, and ESPs are currently used in the various processes 
associated with the glass manufacturing industry. Therefore, an overall control efficiency of at 
least 90 percent is expected and should be applied to emissions estimated using the factor in 
Table 7-2. 4 

7.1.3 Emissions 

Air emissions from glass manufacturing occur in three areas: raw material blending and 
transport, melting, and forming and finishing. Fugitive dust is produced by the blending and 
transport process. In most cases, fabric filters are used on silos and the transport system to 
confine the particulate emissions. Arsenic emissions from the raw material preparation and 
forming and finishing operations are generally considered to be negligible. 

The glass melting furnace is the principal source of arsenic emissions from a glass plant. 
The composition and rate of emissions from glass melting furnaces vary considerably, depending 


7-3 


TABLE 7-2. ARSENIC EMISSION FACTOR FOR GLASS MANUFACTURING 


see 

Number 

Emission Source 

Control 

Device 

Average Emission 
Factor in lb/ton a 

Emission 
Factor Rating 

3-05-014 

Regenerative-type Furnaces 

None 

5.00x10'* 

U 


Source: Reference 4. 

a To convert to kg per metric ton (kg/tonne) multiply by 0.5. 

upon the composition of glass being produced and, to a lesser extent, upon the design and 
operating characteristics of the furnace. Emissions consist primarily of products of combustion 
and entrained PM. One emission factor for uncontrolled arsenic emission from glass 
manufacturing was found and is presented in Table 7-2. Additional sources of information 
include Glass Manufacturing Plants - Background information for Proposed Standards 
(EPA-450/3-79-005a), Summary Report on Emissions from the Glass Manufacturing Industry 
(EPA-600/2-79-101), and The Handbook of Glass Manufacture, 3rd Edition Volume n. 

7.2 Municipal Solid Waste Landfills 

A municipal solid waste (MSW) landfill unit is a discrete area of land or an excavation 
that receives household waste, but is not a land application unit (i.e., for receiving sewage 
sludge). An MSW landfill unit may also receive other types of wastes, such as commercial solid 
waste, nonhazardous sludge, and industrial solid waste. Arsenic emissions from MSW landfills 
are expected to originate from the non-household sources of MSW. 

7.2.1 Process Description 

There are three major designs for municipal landfills: the area method, the trench 
method, and the ramp method. 5 They all utilize a three-step process, which includes spreading 
the waste, compacting the waste, and covering the waste with soil. The area fill method involves 
placing waste on the ground surface or landfill liner, spreading it in layers, and compacting it 
with heavy equipment. A daily soil cover is spread over the compacted waste. The trench 
method entails excavating trenches designed to receive a day’s worth of waste. The soil from the 


7-4 








excavation is often used for cover material and wind breaks. The ramp method is typically 
employed on sloping land, where waste is spread and compacted in a manner similar to the area 
method; however, the cover material obtained is generally from the front of the working face of 
the filling operation. The trench and ramp methods are not commonly used, and are not the 
preferred methods when liners and leachate collection systems are utilized or required by law. 

Modem landfill design often incorporates liners constructed of soil (e.g., recompacted 
clay) or synthetics (e.g., high density polyethylene) or both to provide an impermeable barrier to 
leachate (i.e., water that has passed through the landfill) and gas migration from the landfill. 

7.2.2 Emission Control Techniques 

Landfill gas collection systems are either active or passive systems. Active collection 
systems provide a pressure gradient in order to extract landfill gas by use of mechanical blowers 
or compressors. Passive systems allow the natural pressure gradient created by the increase in 
landfill pressure from landfill gas generation to mobilize the gas for collection. 

Landfill gas control and treatment options include (1) combustion of the landfill gas, and 
(2) purification of the landfill gas. Combustion techniques include techniques that do not recover 
energy (e.g., flares and thermal incinerators) and techniques that recover energy and generate 
electricity from the combustion of the landfill gas (e.g., gas turbines and internal combustion 
engines). Boilers can also be employed to recover energy from landfill gas in the form of steam. 
Flares involve an open combustion process that requires oxygen for combustion; the flares can be 
open or enclosed. Thermal incinerators heat an organic chemical to a high enough temperature in 
the presence of sufficient oxygen to oxidize the chemical to C0 2 and water. Purification 
techniques can also be used to process raw landfill gas to pipeline quality natural gas by using 
adsorption, absorption, and membranes.^ 


7-5 


7.2.3 Emission Factors 


During the development of this document, only one test report was acquired that 
summarized arsenic emissions from a landfill equipped with waste gas flares. An emission 
factor developed from these data is presented in Table 7-3. 6 

7.2.4 Source Locations 

MSW management in the United States is dominated by disposal in landfills. 
Approximately 67 percent of solid waste is landfilled, 16 percent is incinerated, and 17 percent is 
recycled or composted. There were an estimated 5,345 active MSW landfills in the United States 
in 1992. In 1990, active landfills were receiving an estimated 130 million tons of waste annually, 
with 55 to 60 percent reported as household waste and 35 to 45 percent reported as commercial 
waste. 5 

7.3 Asphalt Concrete 

7.3.1 Process Description 

To produce hot-mix asphalt (also referred to as asphalt concrete), aggregate, which is 
composed of gravel, sand, and mineral filler, is heated to eliminate moisture and then mixed with 
hot asphalt cement. The resulting hot mixture is pliable and can be compacted and smoothed. 
When it cools and hardens, hot-mix asphalt provides a waterproof and durable pavement for 
roads, driveways, parking lots, and runways. 

There are three types of hot-mix asphalt plants operating in the United States: batch-mix, 
continuous-mix, and drum-mix. Batch-mix and continuous-mix plants separate the aggregate 
drying process from the mixing of aggregate with asphalt cement. Drum-mix plants combine 
these two processes. Production capacities for all three types of plants range from 40 to 600 tons 


7-6 


TABLE 7-3. ARSENIC EMISSION FACTOR FOR LANDFILL PROCESS GAS 


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7-7 









of hot mix per hour. Almost all plants in operation are of either the batch-mix or drum-mix type. 
Less than 0.5 percent of operating hot-mix plants are of the continuous-mix design. 7 

Aggregate, the basic raw material of hot-mix asphalt, consists of any hard, inert mineral 
material. Aggregate typically comprises between 90 and 95 percent by weight of the asphalt 
mixture. Because aggregate provides most of the load-bearing properties of a pavement, the 
performance of the pavement depends on selection of the proper aggregate. 

Asphalt cement is used as the binding agent for aggregate. It prevents moisture from 
penetrating the aggregate and acts as a cushioning agent. Typically, asphalt cement constitutes 
4 to 6 percent by weight of a hot-mix asphalt mixture. 8 Asphalt cement is obtained from the 
distillation of crude oil. It is classified into grades under one of three systems. The most 
commonly used system classifies asphalt cement based on its viscosity at 140°F (60°C). The 
more viscous the asphalt cement, the higher its numerical rating. 

The asphalt cement grade selected for different hot-mix asphalts depends on the type of 
pavement, climate, and type and amount of traffic expected. Generally, asphalt pavement 
bearing heavy traffic in warm climates requires a harder asphalt cement than pavement subject to 
either light traffic or cold climate conditions. 

Another material used to a greater extent in the production of new or virgin hot-mix 
asphalt is recycled asphalt pavement (RAP), which is pavement material that has been removed 
from existing roadways. RAP is now used by virtually all companies in their hot-mix asphalt 
mixtures. The Surface Transportation Assistance Act of 1982 encourages recycling by providing 
a 5-percent increase in Federal funds to State agencies that recycle asphalt pavement. Rarely 
does the RAP comprise more than 60 percent by weight of the new asphalt mixture. 

Twenty-five percent RAP is typical in batch plants, and 40 to 50 percent RAP mixtures are 
typical in drum-mix plants. 8 

The primary processes of a typical batch-mix hot-mix asphalt facility are illustrated in 
Figure 7-1 1 The moisture content of the stockpiled aggregate at the plant usually ranges from 


7-8 


dia-^wijmiow 



7-9 


Figure 7-1. General Process Flow Diagram for Batch-Mix Asphalt Paving Plants 





















































































































3 to 5 percent. The moisture content of recycled hot-mix asphalt typically ranges from 2 to 
3 percent. The different sizes of aggregate are typically transported by front-end loader to 
separate cold-feed bins and metered onto a feeder conveyor belt through gates at the bottom of 
the bins. The aggregate is screened before it is fed to the dryer to keep oversize material out of 
the mix. 

The screened aggregate is then fed to a rotating dryer with a burner at its lower 
(discharge) end that is fired with fuel oil, natural gas, or propane. In the production of hot-mix 
asphalt, the majority of arsenic emissions can be expected from the rotating dryer. The dryer 
removes moisture from the aggregate and heats the aggregate to the proper mix temperature. 
Arsenic emissions occur primarily from fuel combustion. Aggregate temperature at the discharge 
end of the dryer is about 300°F. The amount of aggregate that a dryer can heat depends on the 
size of the drum, the size of the burner, and the moisture content of the aggregate. As the amount 
of moisture to be removed from the aggregate increases, the effective production capacity of the 
dryer decreases. 

Vibrating screens segregate the heated aggregate into bins according to size. A weigh 
hopper meters the desired amount of the various sizes of aggregate into a pugmill mixer. The 
pugmill typically mixes the aggregate for 15 seconds before hot asphalt cement from a heated 
tank is sprayed into the pugmill. The pugmill thoroughly mixes the aggregate and hot asphalt 
cement for 25 to 60 seconds. The finished hot-mix asphalt is either loaded directly into trucks or 
held in insulated and/or heated storage silos. Depending on the production specifications, the 
temperature of the hot-mix asphalt product mix can range from 225 to 350°F at the end of the 
production process. 

Continuous-mix plants are very similar in configuration to batch plants. Asphalt cement 
is continuously added to the aggregate at the inlet of the mixer. The aggregate and asphalt 
cement are mixed by the action of rotating paddles while being conveyed through the mixer. An 
adjustable dam at the outlet end of the mixer regulates the mixing time and also provides some 
surge capacity. The finished mix is transported by a conveyor belt to either a storage silo or 
surge bin. 8 


7-10 


Drum-mix plants dry the aggregate and mix it with the asphalt cement in the same drum, 
eliminating the need for the extra conveyor belt, hot bins and screens, weigh hopper, and pugmill 
of batch-mix plants. The drum of a drum-mix plant is much like the dryer of a batch plant, but it 
typically has more flights than do batch dryers to increase veiling of the aggregate and to improve 
overall heat transfer. The burner in a drum-mix plant emits a much bushier flame than does the 
burner in a batch plant. The bushier flame is designed to provide earlier and greater exposure of 
the virgin aggregate to the heat of the flame. This design also protects the asphalt cement, which 
is injected away from the direct heat of the flame. 8 

Initially, drum-mix plants were designed to be parallel-flow, as depicted in Figure 7-2. 
Recently, the counterflow drum-mix plant design shown in Figure 7-3 has become popular. The 
parallel flow drum-mix process is a continuous mixing type process using proportioning cold 
feed controls for the process materials. Aggregate, which has been proportioned by gradations, is 
introduced to the drum at the burner end. As the drum rotates, the aggregates and the combustion 
products move toward the other end of the drum in parallel. Liquid asphalt cement flow is 
controlled by a variable flow pump that is electronically linked to the virgin aggregate and RAP 
weigh scales. The asphalt cement is introduced in the mixing zone midway down the drum in a 
lower temperature zone along with any RAP and PM from collectors. The mixture is discharged 
at the end of the drum and conveyed to a surge bin or storage silos. The exhaust gases also exit 
the end of the drum and pass on to the collection system. 7 

In a counterflow drum-mix plant, the material flow in the drum is opposite or counterflow 
to the direction of the exhaust gases. In addition, the liquid asphalt cement mixing zone is 
located behind the burner flame zone so as to remove the materials from direct contact with hot 
exhaust gases. Liquid asphalt cement flow is still controlled by a variable flow pump and is 
injected into the mixing zone along with any RAP and PM from primary and secondary 
collectors. 7 

Of the 3,600 active hot-mix asphalt plants in the United States, approximately 2,300 are 
batch-mix plants, 1,000 are parallel-flow drum-mix plants, and 300 are counterflow drum-mix 
plants. About 85 percent of plants being constructed today are of the counterflow drum-mix 


7-11 



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7-12 


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7-13 


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design; batch-mix plants and parallel-flow drum-mix plants account for 10 percent and 5 percent 
respectively. 7 

7.3.2 Emission Control Techniques 

Emissions of arsenic from hot-mix asphalt plants most likely occur because of fuel 
combustion in the aggregate rotary dryers, but some emissions from the aggregate during the 
drying process are possible. These emissions are most often controlled by wet scrubbers or 
baghouses. 7 

7.3.3 Emission Factors 

Emissions from hot-mix asphalt plants were reexamined recently for the purpose of 
updating AP-42. Representative batch-mix and drum-mix plants (both parallel and counterflow) 
were selected for testing. Emissions from hot-oil heaters used to warm stored asphalt concrete 
were also evaluated. Arsenic emissions from hot-mix plants can result from fuel combustion, 
aggregate mixing and drying, and asphalt heating. The only arsenic emissions found from these 
tests were from the drying process. These arsenic emission factors and two from other source 
testing are provided in Table 7-4. 7,9,10 

7.3.4 Source Locations 

In 1983, there were approximately 2,150 companies operating an estimated 4,500 hot-mix 
asphalt plants in the United States. 8 More recently, the number has fallen to about 3,600 plants. 7 
Approximately 40 percent of these companies operate only a single plant. Plants are usually 
located near the job site, so they are concentrated in areas with an extensive highway and road 
network. 8 Additional information on the location of individual hot-mix asphalt facilities can be 
obtained by contacting the National Asphalt Pavement Association in College Park, Maryland. 


7-14 


TABLE 7-4. ARSENIC EMISSION EACTORS FROM ASPHALT CONCRETE PRODUCTION 


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7-15 











7.4 Abrasive Grain Processing 


Abrasive grain manufacturers produce materials for use by bonded and coated abrasive 
product manufacturers to make abrasive products. 

7.4.1 Process Description 

The most commonly used abrasive materials for abrasive grain manufacturing are silicon 
carbide and aluminum oxides. These synthetic materials account for as much as 80 to 90 percent 
of the abrasive grains produced domestically. Other materials used for abrasive grains are cubic 
boron nitride (CBN), synthetic diamonds, and several naturally occurring minerals such as garnet 
and emery. The use of garnet as an abrasive grain is decreasing. CBN is used for machining the 
hardest steels to precise forms and finishes. The largest application of synthetic diamonds has 
been in wheels for grinding carbides and ceramics. Natural diamonds are used primarily in 
diamond-tipped drill bits and saw blades for cutting or shaping rock, concrete, grinding wheels, 
glass, quartz, gems, and high-speed tool steels. Other naturally occurring abrasive materials 
(including garnet, emery, silica sand, and quartz) are used in finishing wood, leather, rubber, 
plastics, glass, and softer metals. 11 

Silicon carbide is manufactured in a resistance arc furnace charged with a mixture of 
approximately 60 percent silica sand and 40 percent finely ground petroleum coke. A small 
amount of sawdust is added to the mix to increase its porosity so that the CO formed during the 
process can escape freely. Common salt is added to the mix to promote the carbon-silicon 
reaction and remove impurities in the sand and coke. During the heating period, the furnace core 
reaches approximately 4,000°F, at which point a large portion of the load crystallizes. At the end 
of the run, the furnace contains a core of loosely knit silicon carbide crystals surrounded by 
unreacted or partially reacted raw materials. The silicon carbide crystals are removed to begin 
processing into abrasive grains. 

Fused aluminum oxide is produced in pot-type electric arc furnaces with capacities of 
several tons. Before processing, bauxite, the crude raw material, is calcined at about 1,740°F to 


7-16 


remove both free and combined water. The bauxite is then mixed with ground coke (about 
3 percent) and iron borings (about 2 percent). An electric current is applied and the intense heat, 
on the order of 3,700°F, melts the bauxite and reduces the impurities that settle to the bottom of 
the furnace. As the fusion process continues, more bauxite mixture is added until the furnace is 
full. The furnace is then emptied and the outer impure layer is stripped off. The core of 
aluminum oxide is then removed to be processed into abrasive grains. 

CBN is synthesized in crystal form from hexagonal boron nitride, which is composed of 
atoms of boron and nitrogen. The hexagonal boron nitride is combined with a catalyst such as 
metallic lithium at temperatures in the range of 3,000°F and pressures of up to 1,000,000 pounds 
per square inch (psi). 

- Synthetic diamond is manufactured by subjecting graphite in the presence of a metal 
catalyst to pressures in the range of 808,000 to 1,900,000 psi at temperatures in the range of 
2,500 to 4,500°F. 

Figure 7-4 presents a process flow diagram for abrasive grain processing. 11 Abrasive 
grains for both bonded and coated abrasive products are made by graded crushing and close 
sizing of either natural or synthetic abrasives. Raw abrasive materials first are crushed by 
primary crushers and then reduced by jaw crushers to manageable size, approximately 
0.75 inches. Final crushing is usually accomplished with roll crushers that break up the small 
pieces into a usable range of sizes. The crushed abrasive grains are then separated into specific 
grade sizes by passing them over a series of screens. If necessary, the grains are washed in 
classifiers to remove slimes, dried, and passed through magnetic separators to remove 
iron-bearing material before they are again closely sized on screens. This careful sizing is 
necessary to prevent contamination of grades by coarser grains. Sizes finer than 250 grit are 
separated by hydraulic flotation and sedimentation or by air classification. 


7-17 



PM emissions 



© 

A 


i i 



Figure 7-4. Flow Diagram for Abrasive Grain Processes 


Source: Reference 11. 


7-18 























7.4.2 Emission Control Techniques 


Fabric filters preceded by cyclones are used at some facilities to control PM emissions 
from abrasive grain production. This configuration of control devices can attain controlled 
emission concentrations of 37 micrograms per dry standard cubic meter (0.02 grains per dry 
standard cubic foot) and control efficiencies in excess of 99.9 percent. Little other information is 
available on the types of controls used by the abrasives industry to control PM emissions. 
However, it is assumed that other conventional devices such as scrubbers and electrostatic 
precipitators can be used to control PM emissions from abrasives grain and products 
manufacturing. 11 

7.4.3 Emission Factors 

Little information is available on emissions from the manufacture of abrasive grains and 
products. 

Emissions from the production of synthetic abrasive grains, such as aluminum oxide and 
silicon carbide, are likely to consist primarily of PM, PM 10 , and CO from the furnaces. 
Aluminum oxide processing takes place in an electric arc furnace and involves temperatures up 
to 4,710°F with raw materials of bauxite ore, silica, coke, iron borings, and a variety of minerals 
that include chromium oxide, cryolite, pyrite, and silane. This processing is likely to emit 
fluorides, sulfides, and metal constituents of the feed material. 

The primary emissions from abrasive grain processing consist of PM and PM 10 from the 
crushing, screening, classifying, and drying operations. PM is also emitted from materials 
handling and transfer operations. Table 7-5 presents an arsenic emission factor developed from 
the results of a metals analysis conducted on a rotary dryer controlled by a wet scrubber in an 
abrasive grain processing facility. 11 


7-19 


TABLE 7-5. ARSENIC EMISSION FACTOR FOR ABRASIVE GRAIN PROCESSING 


see 

Number 

Emission Source 

Control Device 

Average Emission Factor 
in lb/ton a 

Emission Factor 
Rating 

3-05-035-05 

Rotary Dryer: Sand 
Blasting Grit 

Wet Scrubber 

‘ 2.40x10^ 

E 


Source: Reference 11. 

a Emission factor is expressed in lb of pollutant emitted per ton of grit fed into dryer. To convert to kg per metric ton 
(kg/tonne), multiply by 0.5. 

7.4.4 Source Locations 

The abrasives industry is composed of approximately 400 companies throughout the 
United States engaged in abrasive grain manufacturing, bonded abrasive product manufacturing, 
and coated abrasive product manufacturing. 11 However, the majority of the arsenic emissions 
from abrasive grain manufacturing come from the primary silicon carbide and aluminum oxide 
production facilities, and less than ten of these facilities are currently in operation in the United 
States. 12,13 The locations of these facilities are shown in Table 7-6. 

7.5 Portland Cement Production 

Most of the hydraulic cement produced in the United States is Portland cement—a mixture 
primarily composed of calcium silicates, aluminates, and aluminoferrites. There are four primary 
components in Portland cement manufacturing: raw materials handling, kiln feed preparation, 
pyroprocessing, and finished cement grinding. Pyroprocessing, the fuel intensive process 
accomplished in cement kilns, has been identified as a potential source of arsenic emissions and 
constitutes the primary focus of this chapter. 14 


7-20 








TABLE 7-6. 1995 U.S. PRIMARY ABRASIVE GRAIN MANUFACTURER LOCATIONS 

BY STATE 


State 

No. of Facilities 

Illinois 

1 

Massachusetts 

2 

New York 

3 


Source: References 12,13. 

7.5.1 Process Description 

Figure 7-5 presents a basic flow diagram of the Portland cement manufacturing process. 
The process can be divided into four major steps: raw material acquisition and handling, kiln 
feed preparation, pyroprocessing, and Finished cement grinding. 14 

The initial step in the production of Portland cement manufacturing is raw materials 
acquisition. Calcium, which is the element of highest concentration in Portland cement, is 
obtained from a variety of calcareous raw materials, including limestone, chalk, marl, sea shells, 
aragonite, and an impure limestone known as “natural cement rock.” The other raw 
materials—silicon, aluminum, and iron—are obtained from ores and minerals such as sand, shale, 
clay, and iron ore. Arsenic is expected to be present in the ores and minerals extracted from the 
earth. The only potential source of arsenic emissions from raw material acquisition would be due 
to wind-blown particulate-containing arsenic from the quarry operations. Arsenic emissions are 
expected to be negligible from these initial steps in Portland cement production. 14 

The second step involves preparation of the raw materials for pyroprocessing (thermal 
treatment). Raw material preparation includes a variety of blending and sizing operations 
designed to provide a feed with appropriate chemical and physical properties. The raw material 
processing differs for wet processes and dry processes. At facilities where the dry process is 
used, the moisture content in the raw material, which can range from less than 1 percent to 


7-21 








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7-22 


Figure 7-5. Process Flow Diagram Of Portland Cement Manufacturing Process 









































greater than 50 percent, is reduced to less than 1 percent. Arsenic emissions can occur during 
this drying process, but are anticipated to be very low because the drying temperature is much 
below the boiling point of arsenic. At some facilities, heat for drying is provided by the exhaust 
gases from the pyroprocessor. At facilities where the wet process is used, water is added to the 
raw material during the grinding step, thereby producing a pumpable slurry containing 
approximately 65 percent solids. 14 

Pyroprocessing of the raw material is carried out in the kiln, which is the heart of the 
Portland cement manufacturing process. During pyroprocessing, the raw material is transformed 
into clinkers, which are gray, glass-hard, spherically shaped nodules that range from 0.125 to 
2.0 in. in diameter. The chemical reactions and physical processes that take place during 
pyroprocessing include the following: 

1. Evaporation of uncombined water from raw materials as material temperature 
increases to 212°F. 

2. Dehydration as the material temperature increases from 212°F to approximately 
800°F to form the oxides of silicon, aluminum, and iron. 

3. Calcination, during which carbon dioxide (C0 2 ) is evolved between 1,650°F and 
1,800°F to form calcium oxide. 

4. Reaction of the oxides in the burning zone of the rotary kiln to form cement 
clinker at temperatures of about 2,750°F. 14 

The rotary kiln is a long, cylindrical, slightly inclined, refractory-lined furnace. The raw 
material mix is introduced into the kiln at the elevated end, and the combustion fuels are usually 
introduced into the kiln at the lower end in a countercurrent manner. The rotary motion of the 
kiln transports the raw material from the elevated end to the lower end. A combination of fuels 
such as coal, petroleum coke, or natural gas is used to provide energy for calcination. 
Occasionally, oil, waste plastics, waste solvents, or used oil are used although the use of waste 
solvents is becoming less common. Trace amounts of arsenic are naturally present in coal and 
oil. The use of other materials such as scrap tires is becoming more common. 16 


7-23 


Combustion of fuel during the pyroprocessing step contributes to potential arsenic 
emissions. Arsenic may also be present in the waste-derived fuel mentioned above. Most of the 
arsenic that is volatilized in the hot end of the kiln is expected to condense onto PM upon cooling 
and is either removed in the downstream equipment, such as the APCD, or removed in the 
bypass gases or the preheater. 14 

Pyroprocessing can be carried out using one of five different processes: wet, semi-dry, 
dry, dry with a preheater, and dry with a preheater/precalciner. These processes essentially 
accomplish the same physical and chemical steps described above. The last step in the 
pyroprocessing is the cooling of the clinker. This step recoups up to 30 percent of the heat input 
to the kiln system, locks in desirable product qualities by freezing mineralogy, and makes it 
possible to handle the cooled clinker with conventional conveying equipment. Finally, after the 
cement clinker is cooled, a sequence of blending and grinding operations is carried out to 
transform the clinker into finished Portland cement. 14 

7.5.2 Emission Control Techniques 

With the exception of the pyroprocessing operations, the emission sources in the Portland 
cement industry can be classified as either process emissions or fugitive emissions. The primary 
pollutant resulting from the fugitive sources is PM, which contains a fraction of arsenic. The 
control measures used for these fugitive dust sources are comparable to those used throughout 
the mineral products industries. 

Process fugitive emission sources include materials handling and transfer, raw milling 
operations in dry process facilities, and finish milling operations. Typically, particulate 
emissions from these processes are captured by a ventilation system vented to fabric filters. 
Because the dust from these units is returned to the process, they are considered to be process 
units as well as air pollution control devices. The industry uses shaker, reverse air, and pulse jet 
filters, as well as some cartridge units, but most newer facilities use pulse jet filters. For process 
fugitive operations, the different systems are reported to achieve typical outlet PM loadings of 
0.02 grains per actual cubic foot (gr/acf). 17 Because the arsenic is in particle form, it is expected 


7-24 





that these control devices will have a positive effect on reducing arsenic emissions; however, 
these reductions may not be equivalent to those achieved for overall particulate reduction, since 
arsenic is likely to occur in the smaller size range of particle size distribution. 

In the pyroprocessing units, PM emissions are controlled by fabric filters (reverse air, 
pulse jet, or pulse plenum) and ESPs. The reverse air fabric filters and ESPs typically used to 
control kiln exhausts are reported to achieve outlet PM loadings of 0.02 gr/acf. Clinker cooler 
systems are controlled most frequently with pulse jet or pulse plenum fabric filters. A few gravel 
bed filters have been used on clinker coolers. 14 

7.5.3 Emission Factors 

The principal source of arsenic emissions is expected to be from the kiln. The majority of 
the arsenic input from the raw materials and fuels is incorporated into the clinker. Arsenic 
volatilized from the kiln is either removed in the bypass gases, the preheater, or the APCD. 

Small quantities of emissions would be expected during raw materials processing and mixing in 
the form of fugitive dust containing naturally occurring quantities of arsenic compounds in raw 
materials. 

Processing steps that occur after the calcining process in the kiln would be expected to be 
a much smaller source of emissions than the kiln. Emissions resulting from all processing steps 
include particulate matter. Additionally, emissions from the pyroprocessing step include other 
products of fuel combustion such as sulfur dioxide (S0 2 ), nitrogen oxides (NO x ), carbon dioxide 
(COo), and carbon monoxide (CO). Carbon dioxide from the calcination of limestone will also 
be present in the flue gas. 

Arsenic emissions data for Portland cement kilns with various process, fuel, and control 
configurations were compiled by the U.S. EPA’s Office of Solid Waste in 1994. 15a Testing was 
conducted at 35 Portland cement kilns to certify compliance with the BIF Rule. Emission factors 
developed from the study for dry process kilns and differentiated by fuel and waste type are 
presented in Table 7-7. 18 Table 7-8 presents emission factors for various kiln types. 18 


7-25 


TABLE 7-7. ARSENIC EMISSION FACTORS FOR DRY PROCESS PORTLAND 

CEMENT KILNS BY FUEL AND WASTE TYPE 


see 

Number 

Fuel 

Type 

Waste Type 

Control Device 

Average 
Emission Factor 
in lb/ton a 

Emission 

Factor 

Rating 

3-05-006-06 

Coal 

Solid/Liquid Hazardous 
Waste 

ESP 

1.27x1 O' 4 

D 



None 

Quench Column/FF 

1.22x10’ 5 

D 



Solid/Liquid Hazardous 
Waste 

Quench Column/FF 

1.21xl0* 5 

D 



Solid/Liquid Hazardous 
Waste 

FF 

1.87X10- 6 

D 

3-05-006-06 

Coke 

Liquid Hazardous Waste 

Multiple Cyclone/FF 

1.18xl0‘ 5 

D 


Source: Reference 18. 

3 Emission factor is expressed in lb of pollutant emitted per ton of clinker produced. To convert to kg per metric 
ton (kg/tonne), multiply by 0.5. 

ESP = Electrostatic Precipitator. 

FF = Fabric Filter. 


Additional emission factor data may be available from databases developed by trade associations 
or industry' groups. 19 

7.5.4 Source Locations 

The Portland cement manufacturing industry is dispersed geographically throughout the 
United States. Thirty-six states have at least one facility. As of 1996, there were 109 operating 
Portland cement plants in the United States, operating 202 kilns with a total annual clinker 
capacity of approximately 80 million tons. Table 7-9 presents the name of each Portland cement 
plant and their kiln types and capacities as reported in 1996. 20 


7-26 











TABLE 7-8. ARSENIC EMISSION FACTORS FOR PORTLAND CEMENT MANUFACTURING FACILITIES 


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7-27 












TABLE 7-9. PORTLAND CEMENT PRODUCTION FACILITIES (1995) 


Company 

Location 

No./type of kiln 

Clinker Capacity 
(tons/yr) 

Alabama 

Blue Circle, Inc. 

Calera, AL 

2-dry 

594 

Holnam, Inc. 

Theodore, AL 

1-dry 

1,438 

Lehigh Portland Cement 

Leeds, AL 

1-dry 

700 

Medusa Cement Co. 

Demopolis, AL 

1-dry 

809 

National Cement Co. of Alabama 

Ragland, AL 

1-dry 

944 

Arizona 

Ash Grove Cement Co. 

Foreman, AZ 

3-wet 

883 

California Portland Cement 

Rillito, AZ 

4-dry 

1,150 

Phoenix Cement Co. 

Clarkdale, AZ 

3-dry 

630 

California 

Calaveras Cement Co. 

Redding, CA 

1-dry 

649 

Calaveras Cement Co. 

Tehachapi, CA 

1-dry 

900 

California Portland Cement 

Colton, CA 

2-dry 

748 

California Portland Cement 

Mojave, CA 

1-dry 

1,239 

Kaiser Cement Corp. 

Cupertino, CA 

1-dry 

1,603 

Mitsubishi Cement Corp. 

Lucerne Valley, CA 

1-dry 

1,702 

National Cement Co. of California 

Lebec, CA 

1-dry 

647 

Riverside Cement Co. 

Oro Grande, CA 

7-dry 

1,177 

Riverside Cement Co. 

Riverside, CA 

2-dry 

110 

RMC Lonestar 

Davenport, CA 

1-dry 

799 

Southdown, Inc. 

Victorville, CA 

2-dry 

1,530 

Colorado 

Holnam, Inc. 

Florence, CO 

3-wet 

837 

Holnam, Inc. 

Fort Collins, CO 

1-dry 

496 

Southdown, Inc. 

Lyons, CO 

1-dry 

430 

Eorlda 

Florida Crushed Stone 

Brooksville, FL 

1-dry 

602 

Pennsuco Cement Co. 

Medley, FL 

2-wet 

953 

Rinker Portland Cement Corp. 

Miami, FL 

2-wet 

543 

Southdown, Inc. 

Brocksville, FL 

2-dry 

1,212 

Georgia 

Blue Circle, Inc. 

Atlanta, GA 

2-dry 

614 

Medusa Cement Co. 

Clinchfield, GA 

1-wet. 1-dry 

795 


7-28 














TABLE 7-9. PORTLAND CEMENT PRODUCTION FACILITIES (1995)(CONTINUED) 


Company 

Location 

No./type of kiln 

Clinker Capacity 
(tons/yr) 

Iowa 

Holnam, Inc. 

Mason City, LA 

2-dry 

919 

Lafarge Corp. 

Bufalo, LA 

1-dry 

927 

Lehigh Portland Cement 

Mason City, LA 

1-dry 

804 

Idaho 

Ash Grove Cement Co. 

Inkom, ID 

2-wet 

259 

Illinois 

Centex 

La Salle, LL 

1-dry 

576 

Dixon-Marquette 

Dixon, EL 

4-dry 

521 

Lafarge Corp. 

Grand Chain, IL 

2-dry 

1,159 

Lone Star Industries 

Oglesby, IL 

1-dry 

574 

Indiana 

Essroc Materials 

Logansport, IN 

2-wet 

453 

Essroc Materials 

Speed, IN 

2-dry 

1,013 

Lehigh Portland Cement 

Mitchell, IN 

3-dry 

729 

Lone Star Industries 

Greencastle, LN 

1-wet 

723 

Kansas 

Ash Grove Cement Co. 

Chanute, KS 

2-wet 

484 

Lafarge Corp. 

Fredonia, KS 

2-wet 

384 

Monarch Cement Co. 

Humboldt, KS 

3-dry 

672 

RC Cement Co., Inc. 

Independence, KS 

4-dry 

299 

Kentucky 

Kosmos Cement Co. 

Kosmosdale, KY 

1-dry 

778 

Maryland 

Essroc Materials 

Frederick, MD 

2-wet 

372 

Independent Cement Corp. 

Hagerston, MD 

1-dry 

519 

Lehigh Portland Cement 

Union Bridge, MD 

4-dry 

990 

M^in? 

Dragon Products Co. 

Thomaston, ME 

1-wet 

431 

Michigan 

Holnam, Inc. 

Dundee, MI 

2-wet 

1,054 

Lafarge Corp. 

Alpena, MI 

5-dry 

2,267 

Medusa Cement Co. 

Charlevoix, MI 

1-dry 

1,273 

St. Marvs Cement Corp. 

Detroit, MI 

1-wet 

649 


7-29 














TABLE 7-9. PORTLAND CEMENT PRODUCTION FACILITIES (1995)(CONTINUED) 


Company 

Location 

No./type of kiln 

Clinker Capacity 
(tons/yr) 

Missouri 

Continental Cement Co., Inc. 

Hannibal, MO 

1-wet 

597 

Holnam, Inc. 

Clarksville, MO 

1-wet 

1,297 

Lafarge Corp. 

Sugar Creek, MO 

2-dry 

505 

Lone Star Industries 

Cape Giradeau, MO 

1-dry 

1,188 

RC Cement Co., Inc. 

Festus, MO 

2-dry 

1,269 

Mississippi 

Holnam, Inc. 

Artesia, MS 

1-wet 

476 

Montana 

Ash Grove Cement Co. 

Montana City, MT 

1-wet 

301 

Holnam, Inc. 

Three Forks, MT 

1-wet 

350 

fclevad^ 

Ash Grove Cement Co. 

Louisville, NE 

2-dry 

927 

New M^xicp 

Rio Grande Cement Corp. 

Tijeras, NM 

2-dry 

475 

New York 

Blue Circle, Inc. 

Ravena, NY 

2-wet 

1,692 

Glens Falls Cement Co., Inc. 

Glens Falls, NY 

1-dry 

509 

Independent Cement Corp. 

Catskill, NY 

1-wet 

658 

Ohio 

Lafarge Corp. 

Paulding, OH 

2-wet 

501 

Southdown, Inc. 

Fairborn, OH 

1-dry 

598 

Oklahoma 

Blue Circle, Inc. 

Tulsa, OK 

2-dry 

649 

Holnam, Inc. 

Ada, OK 

2-wet 

598 

Lone Star Industries 

Pryor, OK 

3-dry 

684 

Oregon 

Ash Grove Cement Co. 

Durkee, OR 

1-dry 

524 

Pennsylvania 

Allentown Cement Co., Inc. 

Blandon, PA 

2-dry 

948 

Armstrong Cement & Sup. Corp. 

Cabot, PA 

2-wet 

323 

Essroc Materials 

Nazareth, PA 

1-dry 

1,174 

Essroc Materials 

Nazareth, PA 

4-dry 

583 

Essroc Materials 

Bessemer, PA 

2-wet 

575 


7-30 
















TABLE 7-9. PORTLAND CEMENT PRODUCTION FACILITIES (1995)(CONTINUED) 


Company 

Location 

No./type of kiln 

Clinker Capacity 
(tons/yr) 

Pennsylvania (continued! 

• 



Giant Cemenet Holding, Inc. 

Bath, PA 

2-wet 

601 

Kosmos Cement Co. 

Pittsburgh, PA 

1-wet 

384 

Lafarge Corp. 

Whitehall, PA 

3-dry 

870 

Lehigh Portland Cement 

York, PA 

1-wet 

99 

Medusa Cement Co. 

Wampum, PA 

3-dry 

673 

RC Cement Co., Inc. 

Stockertown, PA 

2-dry 

911 

South Carolina 

Blue Circle, Inc. 

Harleyville, SC 

1-dry 

745 

Giant Cement Holding, Inc. 

Harleyville, SC 

4-wet 

867 

Holnam, Inc. 

Holly Hill, SC 

2-wet 

1,064 

§Qyth Dakota 

Dacotah Cement 

Rapid City, SD 

2-wet, 1-dry 

893 

Tennessee 

RC Cement Co., Inc. 

Chattanooga, TN 

2-wet 

438 

Southdown, Inc. 

Knoxville, TN 

1-dry 

638 

Texas 

Alamo Cement Co. 

San Antonio, TX 

1-dry 

846 

Capitol Aggregates, Inc. 

San Antonio, TX 

1-wet, 1-dry 

839 

Holnam, Inc. 

Midlothian, TX 

1-dry 

1,117 

Lehigh Portland Cement 

Waco, TX 

1-wet 

85 

Lone Star Industries 

Sweetwater, TX 

3-dry 

485 

North Texas Cement 

Midlothian, TX 

3-wet 

851 

Southdown, Inc. 

Odessa, TX 

2-dry 

526 

Sunbelt Cmenet Corp. 

New Braunfels, TX 

1-dry 

980 

Texas Industries 

Midlothian, TX 

4-wet 

1,258 

Texas Industries 

New Braunfels, TX 

1-dry 

847 

Texas-Lehigh Cement Co. 

Buda, TX 

1-dry 

1,103 

Utah 

Ash Grove Cement Co. 

Nephi, UT 

1-dry 

789 

Holnam, Inc. 

Morgan, UT 

2-wet 

317 

Virginia 

Roanoke Cement Co. 

Cloverdale, VA 

1-dry 

946 


7-31 













TABLE 7-9. PORTLAND CEMENT PRODUCTION FACILITIES (1995)(CONTINUED) 


Company 

Location 

No./type of kiln 

Clinker Capacity 
(tons/yr) 

Washington 

Ash Grove Cement Co. 

Seattle, WA 

1-dry 

747 

Holnam, Inc. 

Seattle, WA 

1-wet 

446 

West Virginia 

Capitol Cement Corporation 

Martinsburg, WV 

3-wet 

955 

Centex 

Femley, WV 

2-dry 

480 

Royal Cement Co., Inc. 

Logandale, WV 

1-dry 

195 

Wyoming 

Centex 

Laramie, WY 

2-dry 

644 


Source: Reference 20. 










7.6 Open Burning Of Scrap Tires 


7.6.1 Process Description 

Approximately 240 million vehicle tires are discarded annually. 21 Although viable 
methods for recycling exist, less than 25 percent of discarded tires are recycled; the remaining 
175 million are discarded in landfills, stockpiles, or illegal dumps. 22 Although it is illegal in 
many States to dispose of tires by open burning, fires often occur at tire stockpiles and through 
illegal burning activities. These fires generate a huge amount of heat and are difficult to 
extinguish (some tire fires continue for months). Arsenic is a component of tires and is emitted 
from the combustion of these tires. 

7.6.2 Emission Factors 

Table 7-10 contains emission factors for the open burning of tires. 22 The average 
emission factor presented represents the average of tests performed on the simulated open 
burning of chunk (defined as one-quarter or one-sixth of an entire tire) and shredded tires. When 
estimating emissions from an accidental tire fire, note that emissions from burning tires are 
generally dependent on the bum rate of the tire. A greater potential for emissions exists at lower 
bum rates, such as when a tire is smoldering rather than burning out of control. 22 

Besides accidental or illegal open burning of tires, waste tires are incinerated for energy 
recovery and disposal purposes. Tires are combusted at tire-to-energy facilities, cement kilns, 
tire manufacturing facilities, and as supplemental fuel in boilers. No emission factors for arsenic 
from tire incineration have been located. 

7.6.3 Source Location 

Open burning of scrap tires can occur at permitted landfills that stockpile scrap tires, at 
closed landfills that already contain scrap tires, and at illegal dumpsites where tires are discarded. 


7-33 


TABLE 7-10. ARSENIC EMISSION FACTORS FOR OPEN BURNING OF SCRAP TIRES 


see 

Number 

Emission Source 

Control 

Device 

Average Emission 
Factor in 
. lb/1000 ton a 

Emission 

Factor 

Rating 

5-03-002-03 

Simulated Open Burning of 
Chunk Automobile Tires 

None 

l.OOxlO' 1 

C 


Simulated Open Burning of 
Shredded Automobile Tires 

None 

4.00x10"* 

C 


Source: Reference 23. 

a Emission factors are expressed in lb of pollutant emitted per 1000 ton of waste incinerated. To convert to kg per 
1000 metric tons (kg/1000 tonnes), multiply by 0.907. 

The fires can start by accident or are intentionally set by arsonists, and thus are unpredictable as 
to where and when they will occur. 

7.7 Grain Milling 

Milling is the process of converting grain into flour by mechanical means. The grain is 
cleaned and a small amount of water is added to prevent the outer part of the kernel from 
pulverizing. The moistened grain is mechanically crushed slightly and sheared into chunks. The 
product is sifted to remove the germ and the bran, and the chunks are size separated. The larger 
chunks are recrushed and the intermediate-sized chunks are ground between smooth rolls . 23 
Finally, screens are used to remove undersized and oversized materials, and the final product is 
transferred to the bagging area, to storage, or to bulk load-out. 

The modem milling industry applies many innovations in their process operations. One 
example is the production of free-flowing flour made by agglomerating the flour particles into 
clusters by the addition of moisture and spray-drying. This allows for the separation of high 
protein and high-starch fractions and permits a wide range of custom blending . 24 


7-34 








Limited arsenic emissions data are available for this category. One report from tests 
conducted at a rice milling plant was available for review and emission factors developed from 
that report are presented in Table 7-11. Another test conducted at a feed mill under the 
California AB 2588 (“Hot Spots”) program reported that arsenic was not detected from the 
baghouse discharge or milling operations. 24 

7.8 Process Heaters 

A process heater is similar to an industrial boiler in that heat liberated by the combustion 
of fuels is transferred by radiation and convection to fluids contained in tubular coils. Process 
heaters are used in many chemical manufacturing operations to provide steam and heat input 
essential to chemical processing. They are also used as feed preheaters and as reboilers for some 
distillation operations. The fuels used in process heaters include natural gas, refinery offgases, 
and various grades of fuel oil. Gaseous fuels account for about 90 percent of the energy 
consumed by process heaters. 

There are many variations in the design of process heaters depending on their application. 
In general, the radiant section consists of the bumer(s), the firebox, and tubular coils containing 
the process fluid. Most heaters also contain a convective section in which heat is recovered from 
hot combustion gases by convective heat transfer to the process fluid. 

Process heaters (and boilers) are most applicable where the potential exists for heat 
recovery from the combustion of the vent stream. For example, vent streams with a high VOC 
concentration and high flow rate can provide enough equivalent heat value to act as a substitute 
for fuel that would otherwise be needed. 

Emissions data for this category are limited. Emission factors developed from three 
available test reports are presented in Table T-ll.*" 5,26 ' 2 " 7 


7-35 


TABLE 7-11. ARSENIC EMISSION FACTORS FOR GRAIN MILLING 


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7-36 









TABLE 7-12. ARSENIC EMISSION FACTORS FOR PROCESS HEATERS 


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7-37 










7.9 Cotton Production and Ginning 


Until 1993, arsenic acid (H 3 As0 4 ) was used as a cotton desiccant in some areas of the 
U.S. Its use has contributed to arsenic emissions to the atmosphere both from the field where the 
cotton was grown and from cotton gins. 

Prior to mechanical stripping (harvesting) of cotton, the green leaves must be dried to 
prevent fiber staining and to prevent unacceptable moisture levels in the fiber. Such conditions 
lower the quality of the cotton. In many cotton producing areas a killer frost occurs before 
harvest, thus desiccating the leaves. However, in areas without such a frost, a chemical desiccant 
is needed. Texas and Oklahoma are the primary areas where chemical desiccation has been 
practiced. 

The use of arsenic acid as a cotton desiccant began in 1956 and continued through 1993 
when it was banned from use by the EPA. 28 In practice, about 3 pints of arsenic acid per acre 
was applied by ground or aerial spraying. It has been estimated that only about 5 percent of the 
arsenic acid reached the intended crop. The remaining overspray either drifted from the field or 
was deposited in field soil. 

Sources of potential arsenic emissions to the atmosphere have included application 
overspray; arsenic-containing dust and plant matter emitted during harvesting; arsenic-containing 
dust, plant matter, and lint emitted during ginning; and wind blown soil from fields where 
spraying has been conducted. 29 

Since the use of arsenic acid as a cotton desiccant has been banned, the emissions 
potential has been largely eliminated. In some areas where spraying has occurred over many 
years, it is possible that arsenic accumulated in the soils could still be emitted as windblown dust. 
However, that potential will continue to diminish over time. 

Limited arsenic emissions data for cotton ginning were available in the literature; 
however, these data are eighteen to twenty years old, and were generated from tests at a cotton 


7-38 




gin which received cotton treated with arsenic acid. The ginning process has changed since that 
time, and the data are deemed no longer applicable and are therefore not included in this 
document. 



7-39 


References for Section 7.0 


1. Eastern Research Group, Inc. Clean Air Act, Section 112(k) Candidate Pollutants , draft 
report. Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
Office of Air Quality Planning and Standards, Visibility and Ecosystem Protection 
Group, 1996. 

2. U.S. EPA. Compilation of Air Pollutant Emission Factors , 5th ed. (AP-42), Vol. I: 
Stationary Point and Area Sources, Section 11.15: Glass Manufacturing. Research 
Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office of Air 
Quality Planning and Standards, 1995. 

3. Drake, R A. Glass Technical Institute. San Diego, CA. Letter to Dennis Beauregard. 
U.S. U.S. Environmental Protection Agency. Research Triangle Park, North Carolina, 
October 1997. 

i 

4. Factor Information Retrieval System Version 4.0 (FIRE 4.0). Research Triangle Park, 
North Carolina: U.S. Environmental Protection Agency, September 1995. 

5. AP-42, 5th ed., op. cit., note 2. Section 2.4, Landfills, 1995. 

6. California Air Resources Board. Source Emissions Testing of Landfills Boiler and Flare 
System. Confidential Report No. ERC-3. 

7. AP-42, 5th ed., op. cit., note 2. Section 11.1, Mineral Products Industry, 1995. 

8. U.S. EPA. Second Review of New Source Performance Standards for Asphalt Concrete 
Plants. EPA-450/3-85-024. Research Triangle Park, North Carolina: 

U.S. Environmental Protection Agency, Office of Air Quality Planning and Standards, 
October 1985. 

9. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 724. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

10. Factor Information Retrieval System Version 3.0 (FIRE 3.0), Record Number 247. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, 
September 1994. 

11. AP-42, 5th ed., op cit., note 2. Section 11.31, Bonded Abrasive Products, 1995. 

12. Holston, R. (Radian International, LLC) and G. Pressbury (U.S. Department of 
Commerce). Telecon. March 22, 1996. 


7-40 



13. Holston, R. (Radian International, LLC) and A. Wherry (Abrasive Grain Association). 
Telecon. March 22, 1996. 

14. AP-42, 5th ed., op. cit., note 2. Section 11.6, Portland Cement Manufacturing, 1995. 

15. U.S. Environmental Protection Agency. Emission Factor Documentation for AP-42, 
Section 11.6, Portland Cement Manufacturing. Research Triangle Park, North Carolina. 
1995. 

16. Hawkins, G. Potland Cement Association. Skokie, Dinois. Letter to Dennis Beauregard. 
U.S. Environmental Protection Agency. Research Triangle Park, North Carolina. 

October 31, 1997 

17. U.S. EPA. Locating and Estimating Air Emissions from Sources of Lead and Lead 
Compounds, Draft. Research Triangle Park, North Carolina: U.S. Environmental 
Protection Agency, June 1995. 

18. U.S. EPA. Technical Support for Revision of the Hazardous Waste Combustion 
Regulations for Cement Kilns and Other Thermal Treatment Devices, Second Draft. 
Prepared by Energy and Environmental Research Corporation, Irvine, California, 
W T ashington, D.C.: U.S. Environmental Protection Agency, Office of Solid Waste, 

May 17, 1994. 

19. Rigo, H.G. Rigo & Rigo Associates, Inc., Berea, OH. Teleconference with 

P. Marsosudiro, Eastern Research Group, Morrisville, North Carolina. April 6, 1998. 

20. Portland Cement Association. U.S. and Canadian Portland Cement Industry: Plant 
Information Summary. Skokie, IL: Portland Cement Association, 1996. 

21. Lemieux, P.M. and J.V. Ryan. Characterization of Air Pollutants Emitted from a 
Simulated Scrap Tire Fire. Journal of the Air and Waste Management Association, 
43(#)pp. 1106-1115, August 1993. 

22. AP-42, 5th ed., op. cit., note 2. Section 2.5, Open Burning, 1995. 

23. Austin, G.T. Shreve's Chemical Process Industries, 5th edition, Chapter 25: Food and 
Food By-Product Processing Industries. 1984. pp. 446-447. 

24. Hargrove, K.L., Farmer's Rice Cooperative, to R. A. Isom, Fresno County. Transmittal of 
AB-2588 Air Toxics Emission Report. Rice Drying. September 11, 1990. 

25. Radian 1993. TOX_D_EF, Record 324, Composite of 24 tests on 8 units; CARB 2588 
data. June 11, 1995. 


7-41 


26. Pope & Steiner Environmental Services for Texaco Trading and Transportation, Inc. 
AB-2588 Testing at Texaco Trading and Transportation, Inc. Panoche Station, 

Volumes I, II, and HI. Report PS-90-2187. (WSPA) September 1990. 

27. Southern California Edison Company. Emissions Inventory Testing at Huntington Beach 
Generating Station, Fuel Oil Heater No. 2. CARNOT. Rosemead, California. 

May 1990. 

28. Federal Register, Volume 58, No. 139. Thursday, July 22, 1993. p. 39205. Arsenic 
Acid; Receipt of Request to Cancel; Cancellation Order. U.S. Environmental Protection 
Agency. 58 FR 39205. 

29. U.S. EPA. Preliminary Study of Sources of Inorganic Arsenic. EPA-450/5-82-005. 
Research Triangle Park, North Carolina: U.S. Environmental Protection Agency, Office 
of Air Quality Planning and Standards, August 1982. 


7-42 



SECTION 8.0 

SOURCE TEST PROCEDURES 


Arsenic emissions can be measured by a number of methods. The following methods are 
applicable for measuring emissions of arsenic in ambient air and arsenic contained in stack gas 
emissions: (1) National Institute of Occupational Safety and Health (NIOSH) Method 7300, 1 
(2) NIOSH Method 7900, 2 (3) NIOSH Method 7901(4) NIOSH Method 5022, 3 (5) EPA’s 
Methodology for the Determination of Suspended Particulate Matter in the Atmosphere 
(High-Volume Method), Appendix B, and Appendix G modified Methodology for the 
Determination of Lead in Suspended Particulate Matter Collected From Ambient Air 
(40 CFR 50), 4 (6) EPA Method 29, 5 (7) EPA Method 108, 6 (8) EPA BIF Method, Section 3.0, 7 
(9) California Air Resources Board (CARB) Method 423, 8 and (10) CARB Draft Method 436m. 9 

All of the NIOSH methods and EPA 40 CFR 50 Appendixes apply to the collection and 
analysis of arsenic from ambient air. EPA Method 29 and BIF, Section 3.0, are part of the Boiler 
and Industrial Furnace (BEF) Regulations and are used to sample for total inorganic and organic 
arsenic, and other metals, in stack gases. EPA Method 108 and CARB Method 423 are used to 
sample specifically for inorganic and organic arsenic in stack gases. CARB Draft Method 436 is 
used to sample for total inorganic and organic arsenic, and other metals, in stack gases. 

Sections 8.1 and 8.2 of this report summarize the field sampling procedures for 
measuring arsenic in ambient air and stack gases, respectively. Section 8.3 describes the 
different analytical techniques used to analyze and measure the amount of arsenic collected in 
ambient air and stack gas samples. 


8-1 


8.1 Ambient Air Sampling Methods 


Ambient air concentrations of arsenic can be measured using Methodology for the 
Determination of Suspended Particulate Matter in the Atmosphere (High-Volume Method) and 
modified Methodology for the Determination of Lead in Suspended Particulate Matter Collected 
From Ambient Air; and NIOSH Methods 7300, 7900, 7901 and 5022. The following methods 
are described in detail below. 

8.1.1 Methodology for the Determination of Suspended Particulate Matter in the Atmosphere 
(High-Volume Method) and Modified Methodology for the Determination of Lead in 
Suspended Particulate Matter Collected from Ambient Air 

A high Volume sampler is used to collect total suspended particulate (TSP) matter. 

Figure 8-1 shows a simplified diagram of the components of the high-volume ambient air 
sampling equipment. 10 The equipment is mounted in an enclosed shelter equipped with a roof. 
Ambient air is drawn under the roof of the shelter through a pre-weighed glass-fiber filter. The 
high-volume sampler should be operated for 24 hours at an average flow rate of 1.7 cubic meters 
per minute (m 3 /min). The approximate concentration range of the method is 2 to 750 pg/m 3 . 
However, the lower limit is determined by the sensitivity of the balance used in the analysis by 
the laboratory, and the upper limit is affected by various factors, such as variability of filters used 
in the sampler, and particle size distribution of the sample. 

After sampling, the filter is removed and sent to a laboratory for analysis. The method is 
then modified to prepare and analyze the high-volume filter sample for arsenic instead of lead. 
The filter is weighed several times until a constant weight is obtained and then the filter is 
digested in an acid solution and analyzed for total arsenic content either by atomic absorption 
spectrophotometry (AAS) or inductively coupled plasma (ICP) emission spectroscopy. 


8-2 


Glass Fiber Filter 



Figure 8-1. Components of a High-Volume Ambient Air Sampler for Arsenic 
Source: Reference 10. 


8-3 


ERG LE3.Cdi 




















































One advantage of the High-Volume Method (Appendix B) and the Appendix G Modified 
Lead Method is that the ambient air sample is collected over a 24-hour period, which can 
encompass all types of weather conditions, particularly temperature changes, and the range of 
emission source activities that occur throughout a 24-hour period. 

One disadvantage of the high-volume sampling method is that it was designed for 
sampling only total inorganic arsenic compounds in suspended particulate matter (PM). 

Inorganic arsenic cannot be speciated and most organic arsenic compounds cannot be detected. 

A second disadvantage is that the high-volume method is very dependent on meteorological 
conditions. Any change in wind speed or direction and any amount of precipitation can influence 
the sample results. To interpret the effects of weather conditions on the sample results, 
meteorological data must be recorded during the sampling period. 

8.1.2 NIOSH Method 7300 - Methodology for the Determination of Elements by Inductively 

Coupled Plasma (ICP) 

Method 7300 can be used to sample for elemental arsenic and various metals in ambient 
air. This method collects particulate metals only. Samples are collected on a mixed cellulose 
ester membrane filter (MCEF), 0.8 pm pore size, 37 mm diameter, with a backup pad, placed 
into a cassette filter holder. A calibrated personal sampling pump is used to pull air through the 
cassette holder at a flow rate between 1 and 4 L/min for a total sample size of 200 to 2,000 L. 

The filters and backup pads, housed inside the cassette, are sent to the laboratory for 
analysis. At the laboratory, the filters are ashed using a nitric acid/perchloric acid solution and 
diluted to a known final volume. After the initial sample preparation step, samples are analyzed 
by ICP or AAS at the specific wavelength for arsenic analysis. 

Samples collected using NIOSH 7300 are relatively stable, but it is important not to 
exceed a filter loading of approximately 2 mg of total dust. 


8-4 




8.1.3 NIOSH Method 7900 - Methodology for the Determination of Arsenic and Compounds, 

as Arsenic, using Direct-Aspiration (Flame) Atomic Absorption Spectroscopy (AAS) 

Method 7900 can be used to sample for arsenic in ambient air. This method collects only 
particulate arsenic and is an elemental analysis, not compound specific. Samples are collected on 
a MCEF, 0.8 pm pore size, 37 mm diameter, with a backup pad, placed into a cassette filter 
holder. A calibrated personal sampling pump is used to pull air through the cassette holder at a 
flow rate of between 1 and 3 L/min for a total sample size of 30 to 1,000 L. 

The filters and backup pads, housed inside the cassette, are sent to the laboratory for 
analysis. At the laboratory, the filters are ashed using a nitric acid/perchloric acid solution and 
diluted to a known final volume. After the initial sample preparation step, samples are analyzed 
for arsenic by direct-aspiration (flame) AAS. 

Samples collected using NIOSH 7900 are relatively stable if refrigerated, but it is 
important not to exceed a filter loading of approximately 2 mg total dust. Again, this method 
collects particulate arsenic only and not volatile organic arsenic compounds, such as arsenic 
trioxide. 

8.1.4 NIOSH Method 7901 - Methodology for the Determination of Arsenic Trioxide, as 

Arsenic, by Graphite Furnace Atomic Absorption (GFAA) 

Method 7901 can be used to sample for particulate arsenic compounds as well as arsenic 
trioxide vapor. Samples are collected on treated MCEFs, 0.8 pm pore size, 37 mm diameter, and 
a cellulose backup pad, placed into a cassette filter holder. The filter and backup pad is 
previously treated with a sodium carbonate/glycerol solution. A calibrated personal sampling 
pump is used to pull air through the cassette holder at a flow rate of between 1 and 3 L/min for a 
total sample size of 30 to 1,000 L. 

The filters and backup pads, housed inside the cassette, are sent to the laboratory for 
analysis. At the laboratory, the filters and backup pads are digested on a hot plate using 


8-5 


concentrated nitric acid and 30 percent hydrogen peroxide. The samples are then diluted to a 
known final volume. After the initial sample preparation step, samples are analyzed for arsenic 
by GFAA. 

Samples collected using NIOSH 7901 are relatively stable, but it is important not to 
exceed a filter loading of approximately 2 mg total dust. 

8.1.5 NIOSH Method 5022 - Methodology for the Determination of Organo-Arsenic 

Compounds by Ion Chromatography (IC)/Graphite Furnace Atomic Absorption (GFAA) 

Method 5022 can be used to sample for particulate organo-arsenic compounds. Samples 
are collected on a polytetrafluoroethylene (PTFE) backed membrane filter, 1 pm pore size, 

37 mm diameter, with a backup pad, placed into a cassette filter holder. A calibrated personal 
sampling pump is used to pull air through the cassette holder at a flow rate between 1 and 
3 L/min for a total sample volume of 50 to 1,000 L. 

The filters and backup pads, housed inside the cassette, are sent to the laboratory for 
analysis. At the laboratory, the filter is sonicated and extracted in a sodium carbonate/sodium 
bicarbonate/sodium borohydride solution. The samples are then analyzed for organo-arsenic 
compounds by IC/GFAA. 

8.2 Stationary Source Sampling Methods 

Various methods are available for sampling stack gas concentrations of arsenic: EPA 
Method 29, EPA Method 108, EPA BEF Method, and CARB Methods 423 and Draft 436. These 
methods are described in this section. 


8-6 




8.2.1 EPA Method 29 - Determination of Metals Emissions from Stationary Sources 

EPA Method 29 can be used to sample PM and total inorganic and organic arsenic 
compounds isokinetically from stack gases. The sampling train for Method 29 is a modification 
of the EPA Method 5 11 sampling train, and is shown in Figure 8-2. 12 

Particulate arsenic with a particle size diameter greater than or equal to 0.3 pm is 
collected through a glass nozzle and probe onto a pre-weighed glass fiber filter. Particulate 
arsenic with a particle size diameter less than 0.3 pm and arsenic compounds in the vapor phase 
pass through the filter and are collected in a dilute nitric acid/hydrogen peroxide solution 
contained in the train impingers. The nozzle/probe and both halves of the filter holder are 
washed with dilute nitric acid. The nozzle/probe wash, two separate filter holder washes, filter, 
and impinger solution are sent to a laboratory, where they are digested in an acid solution and 
analyzed for arsenic content either by AAS or ICP. The samples collected on the filter and in the 
impinger solution can be analyzed separately to differentiate between the amount of particulate 
arsenic and arsenic in the gaseous phase. 

The exact run time and volume sampled varies from source to source depending on the 
required detection limit. Typically, the Method 29 train is run for 2 hours and collects 
approximately 2.55 m 3 of stack gas. According to the method, the ICP analytical detection limit 
is 53 ng/ml of total arsenic, and the GFAA analytical detection limit is 1 ng/ml. The upper range 
can be extended considerably by diluting the sample prior to analysis. However, actual sample 
analytical detection limits are sample dependent and may vary due to the sample matrix. Also, 
laboratory instrumentation may affect the detection limit. 

Although it is the preferred method for sampling stack gas streams and can measure 
several metals at one time, the method cannot be used to speciate inorganic or organic arsenic 
compounds. 


8-7 



Glass Filter Holder Thermometer 


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8-8 


Figure 8-2. EPA Method 29, BIF Method, and CARB Draft Method 436 

Sampling Train 










































































































8.2.2 EPA Method 108 - Methodology for the Determination of Particulate and Gaseous 

Arsenic Emissions 

EPA Method 108 can be used to sample PM and total inorganic and organic arsenic 
compounds isoldnetically from stack gases. The Method 108 sampling train is a modified EPA 
Method 5 sampling train and is shown in Figure 8-3. 8 

Particulate arsenic with a particle size diameter greater than or equal to 0.3 pm is 
collected through a glass nozzle and probe onto a pre-weighed glass fiber filter. Particulate 
arsenic with a particle size diameter less than 0.3 pm and arsenic compounds in the vapor phase 
pass through the filter and are collected in deionized water contained in the train impingers. The 
nozzle/probe, front half of the filter housing, and glassware containing the impinger solution are 
washed with a sodium hydroxide solution. The washes, filter, and impinger solution are sent to a 
laboratory, where they are digested in an acid solution and analyzed for arsenic content either by 
AAS or ICP. The samples collected on the filter and in the impinger solution can be analyzed 
separately to differentiate between the amount of particulate arsenic and gaseous arsenic. 

The exact run time and volume sampled varies from source to source depending on the 
required detection limit. Actual sample analytical detection limits are sample dependent and may 
vary due to the sample matrix. Also, laboratory instrumentation may affect the detection limit. 

8.2.3 EPA BEF Method Section 3.0 - Methodology for the Determination of Metals Emissions 

in Exhaust Gases from Hazardous Waste Incineration and Similar Combustion Processes 

The EPA BEF method can be used to sample PM and total inorganic and organic arsenic 
compounds isokinetically from stack gases. The BIF method sampling train is a modified EPA 
Method 5 sampling train, and is identical to the Method 29 sampling train, and is shown is 
Figure 8-2. 

The EPA BEF Method sampling, analytical procedures, and analytical detection limits are 
identical to Method 29; refer to Section 8.2.1 for the discussion. 


8-9 


Temperature 

Sensor 



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8-10 


Figure 8-3. EPA Method 108 and CARB Method 423 Sampling Train 













































































8.2.4 CARB Method 423 - Methodology for the Determination of Particulate and Gaseous 

Inorganic Arsenic Emissions from Stationary Sources 

CARB Method 423 can be used to sample PM and total inorganic and organic arsenic 
compounds isokinetically from stack gases. The Method 423 sampling train is similar to EPA 
Method 5 sampling train, and is identical to the Method 108 sampling train, see Figure 8-3. 

CARB Method 243 sampling and analytical procedures are identical to Method 108; refer 
to Section 8.2.2 for the discussion. 

8.2.5 CARB Draft Method 436 - Determination of Multiple Metals Emissions from Stationary 

Sources 

Draft Method 436 can be used to sample PM and total inorganic and organic arsenic 
compounds isokinetically from stack gases. The sampling train for Draft Method 436 is a 
modification of the EPA Method 5 sampling train, and is identical to EPA Method 29 (see 
Figure 8-2). 

Draft Method 436 sampling, analytical procedures, and analytical detection limits are 
identical to EPA Method 29; refer to Section 8.2.1 for the discussion. 

8.3 Analytical Techniques For The Measurement Of Arsenic 

The most common technique for measuring total arsenic in samples is spectroscopy. The 
two spectroscopic techniques used most by environmental laboratories are AAS and ICP. AAS 
is the most common method used to measure total arsenic. The advantages to AAS are that the 
method is simple, rapid, and applicable to a large number of metals. Samples other than drinking 
water must be acid-digested prior to analysis. Three types of AAS methods for measuring total 
arsenic are direct aspiration (flame), graphite furnace, and hydride-generation. 


8-11 


The second most common technique for measuring total arsenic in samples is ICP, which 
allows simultaneous, or sequential, determination of several metals in a sample during a single 
analytical measurement. Samples must be acid-digested prior to analysis. 

Although not as common, another technique for measuring arsenic in samples is ion 
chromatography (IC) connected to GFAA. 

8.3.1 Direct Aspiration (Flame) Atomic Absorption Spectroscopy (AAS) 

Method 7000 13 specifies the procedure for analyzing samples using direct-aspiration 
(flame) AAS. In direct-aspiration (flame) AAS, a sample is aspirated and atomized in an 
air/acetylene flame. A light beam from a hollow cathode lamp, whose cathode is made of the 
element being measured, is directed through the flame into a monochromator, and onto a detector 
that measures the amount of light absorbed. Absorption depends upon the presence of free, 
unexcited ground-state atoms in the flame. Because the wavelength of the light beam is 
characteristic of only the element being measured, the light energy absorbed by the flame is a 
measure of the concentration of that element in the sample. With flame AAS, if the proper flame 
and analytical conditions are not used, chemical and ionization interferences can occur. Flame 
AAS in normally performed as a single element analysis. If direct-aspiration (flame) AAS 
techniques do not provide adequate sensitivity, graphite furnace techniques can be used. 

8.3.2 Graphite Furnace Atomic Absorption (GFAA) Spectroscopy 

Method 7060 13 specifies the procedure for analyzing samples for total arsenic using 
graphite furnace AAS. The principal of graphite furnace AAS is essentially the same as for 
direct-aspiration (flame) AAS, except a furnace rather than a flame is used to atomize the sample. 
In graphite furnace AAS, a representative aliquot of a sample is placed in a graphite tube in the 
furnace, evaporated to dryness, charred, and atomized. The radiation from a given excited 
element is passed through the vapor containing ground-state atoms of that element. The intensity 
of the transmitted radiation decreases in proportion to the amount of the ground-state element in 
the vapor. The metal’s atoms to be measured are placed in the beam of radiation by increasing 


8-12 


the temperature of the furnace, thereby causing the injected sample to be volatilized. A 
monochromator isolates the characteristic radiation from the hollow cathode lamp or 
electrodeless discharge lamp, and a photosensitive device measures the attenuated transmitted 
radiation. 

The major advantage of GFAA is that it affords extremely low detection limits. It is the 
easiest technique to perform on relatively clean samples. Because this technique is so sensitive, 
however, interferences can be a problem; finding the optimum combination of digestion, heating 
times, and temperatures, and matrix modifiers can be difficult for complex matrices. 

8.3.3 Inductively Coupled Plasma (ICP) Atomic Emission Spectroscopy 

Method 6010 13 specifies the procedures for analyzing samples using ICP. The ICP 
method measures element-emitted light by optical spectrometry. The sample is nebulized and the 
resulting aerosol is transported to the plasma torch, where excitation occurs. Characteristic 
atomic-line emission spectra are produced by radio-frequency inductively coupled plasma. The 
spectra are dispersed by a grating spectrometer, and the intensities of the lines are monitored by 
photomultiplier tubes. The photocurrents from the photomultiplier tubes are processed and 
controlled by a computer. 

The primary advantage of ICP is that it allows simultaneous or rapid sequential 
determination of many elements in a short time. The primary disadvantage is background 
radiation from other elements and the plasma gases. Although all ICP instruments utilize 
high-resolution optics and background correction to minimize these interferences, analysis for 
traces of metals in the presence of a large excess of a single metal is difficult. 

8.3.4 Hydride Generation Atomic Absorption (HGAA) Spectroscopy 

Method 7061 13 specifies the procedure for analyzing samples for total arsenic using 
HGAA. HGAA utilizes a chemical reduction to reduce and separate arsenic selectively from a 
digested sample along with standard AAS techniques. 


8-13 


The primary advantage of this technique is that arsenic can be isolated and quantitated 
from complex samples. 

A disadvantage of HGAA is that significant interferences will occur when easily reduced 
metals are present, and/or when high concentrations of transition metals are present. Also, 
oxidizing agents, such as oxides of nitrogen, may remain after the sample has been digested. 

8.3.5 Ion Chromatography (IC)/GFAA 

NIOSH Method 5022 specifies the procedure for analyzing air samples for total arsenic 
using an IC connected to GFAA. Ion chromatography is a separation technique used for the 
analysis of ionic species. Separation of components in a sample can be achieved with the use of 
a mobile phase (eluent), and a stationary phase (a specific type of polymeric resin bed inside of a 
column). A sample analyte is introduced into the flowstream of the mobile phase (eluent) and is 
carried onto the stationary phase (column). The analyte then undergoes a separation process 
based on its affinity for either of the mobile or stationary phases. 

With NIOSH Method 5022, the IC detector is bypassed, and the sample flows into an 
arsine generator where gaseous arsines are formed. A gas-liquid separator is then used to flow 
the sample into the GFAA where the sample is quantitated. 


8-14 


References for Section 8.0 


1. National Institute for Occupational Safety and Health. NIOSH Method 7300. NIOSH 
Manual of Analytical Methods, 3rd edition. Cincinnati, Ohio: U.S. Department of 
Health, Education, and Welfare, February 15, 1984. 

2. National Institute for Occupational Safety and Health. NIOSH Method 7900. NIOSH 
Manual of Analytical Methods, 3rd edition. Cincinnati, Ohio: U.S. Department of 
Health, Education, and Welfare, August 15, 1987. 

3. National Institute for Occupational Safety and Health. NIOSH Method 5022. NIOSH 
Manual of Analytical Methods, 3rd edition. Cincinnati, Ohio: U.S. Department of 
Health, Education, and Welfare, May 15, 1985. 

4. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, Part 50, 
Appendix B—Reference Method for the Determination of Suspended Particulate Matter in 
the Atmosphere (High-volume Method). Washington, D.C.: U.S. Government Printing 
Office,-1994. 

5. U.S. EPA. Methodology for the Determination of Metals Emissions in Exhaust Gases 
from Hazardous Waste Incineration and Similar Combustion Sources, 3rd ed., Test 
Methods for Evaluating Solid Waste: Physical/Chemical Methods, Method 12. SW-846. 
Washington, D.C.: U.S. Environmental Protection Agency, Office of Solid Waste and 
Emergency Response, September 1988. 

6. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, Part 61, 
Appendix B—Method 108, Determination of Particulate and Gaseous Arsenic Emissions. 
Washington, D.C.: U.S. Government Printing Office, 1991. 

7. U.S. EPA. Test Methods for Evaluating Solid Waste. Report No. SW-846. EPA Draft 
Method 0012 - Multi-Metal Train. EPA/530-SW-91-010. U.S. Environmental Protection 
Agency, Office of Solid Waste, December 1990. 

8. California Air Resources Board. Stationary Source Test Methods, Volume III: Methods 
for Determining Emissions of Toxic Air Contaminants from Stationary Sources. 

Method 423. Sacramento, CA: California Air Resources Board, September 12, 1987. 

9. California Air Resources Board. Stationary Source Test Methods, Volume III: Methods 
for Determining Emissions of Toxic Air Contaminants from Stationary Sources. 

Method 436. Sacramento, CA: California Air Resources Board, March 24, 1992. 

10. U.S. EPA. APTI Course 435 Atmospheric Sampling, Student Manual. 

EPA 450/2-80-004. Research Triangle Park, North Carolina: U.S. Environmental 
Protection Agency, September 1980. pp. 4-38 and 4-51. 


8-15 


11. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, Part 60, 
Appendix B--Method 29, Determination of Metals Emissions from Stationary Sources. 
Washington, D.C.: U.S. Government Printing Office, 1994. 

12. U.S. Code of Federal Regulations. Title 40, Protection of the Environment, Part 60, 
Appendix A: Methodology for the Determination of Metals Emissions in Exhaust Gases 
from Incineration and Similar Combustion Sources (Draft), Method 29. Washington, 
D.C.: U.S. Government Printing Office, 1992. 

13. U.S. EPA. Test Methods for Evaluating Solid Waste , Volume LA: Lab Manual of 
Physical/Chemical Methods. Report No. SW-846. U.S. Environmental Protection 
Agency, September 1986. 


8-16 




APPENDIX A 


EMISSION FACTOR SUMMARY TABLE 




























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TABLE A-l. SUMMARY OF EMISSION FACTORS BY SOURCE CLASSIFICATION CODES 


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A-14 















TECHNICAL REPORT DATA 

(PLEASE READ INSTRUCTIONS ON THE REVERSE BEFORE COMPLETING) 

1. REPORT NO. 2. 

EPA-454/R-98-013 

3. RECIPIENTS ACCESSION NO. 

4. TITLE AND SUBTITLE 

LOCATING AND ESTIMATING AIR EMISSION FROM SOURCES OF 
ARSENIC AND ARSENIC COMPOUNDS 

6. REPORT DATE 

6/1/98 

«. PERFORMING ORGAMZATION CODE 

7. AUTHOR(S) 

1. PERFORMING ORGANIZATION REPORT NO. 

9. PERFORMING ORGANIZATION NAME AND ADDRESS 

EASTERN RESEARCH GROUP, INC 

P 0 BOX 2010 

MORRISVILLE, NC 27560 

10. PROGRAM ELEMENT NO. 

11. CONTRACT/GRANT NO. 

68-D7-0068 

12. SPONSORING AGENCY NAME AND ADDRESS 

U. S. ENVIRONMENTAL PROTECTION AGENCY 

OFFICE OF AIR QUALITY PLANNING AND STANDARDS (MD-14) 

RESEARCH TRIANGLE PARK, NC 27711 

13. TYPE OF REPORT AND PERIOD COVERED 

FINAL 

14. SPONSORING AGENCY CODE 

15. SUPPLEMENTARY NOTES 

EPA WORK ASSINGMENT MANAGER: DENNIS BEAUREGARD (919) 541-5512 

16. ABSTRACT 

TO ASSIST GROUPS INTERESTED IN INVENTORYING AIR EMISSIONS OF VARIOUS POTENTIALLY TOXIC 
SUBSTANCES, THE U.S. ENVIRONMENTAL PROTECTION AGENCY IS PREPARING A SERIES OF DOCUMENTS, 
SUCH AS THIS, TO COMPILE AVAILABLE INFORMATION ON SOURCES AND EMISSIONS OF THESE 

SUBSTANCES. THIS DOCUMENT DEALS SPECIFICALLY WITH ARSENIC AND ARSENIC COMPOUNDS. ITS 
INTENDED AUDIENCE INCLUDES, FEDERAL, STATE, AND LOCAL AIR POLLUTION PERSONNEL AND OTHERS 
INTERESTED IN LOCATING POTENTIAL EMITTERS OF ARSENIC AND IN MAKING GROSS ESTIMATES OF AIR 
EMISSIONS THEREFROM. 

THIS DOCUMENT PRESENTS INFORMATION ON (1) THE TYPES OF SOURCES THAT MAY EMIT ARSENIC; (2) 
PROCESS VARIATIONS AND RELEASE POINTS FOR THESE SOURCES; AND (3) AVAILABLE EMISSIONS 
INFORMATION INDICATING THE POTENTIAL FOR ARSENIC RELEASES INTO THE AIR FROM EACH OPERATION. 

17. KEY WORDS AND DOCUMENT ANALYSIS 

a. DESCRIPTORS 

ARSENIC 

AIR EMISSION SOURCES 

TOXIC SUBSTANCES 

EMISSION ESTIMATION 

b. IDENTIFIERS/OPEN ENDED TERMS 

c. COSAT! FIELD/GROUP 

18. DISTRIBUTION STATEMENT 

UNLIMITED 

UNCLASSIFIED 

21. NO. OF PAGES 

278 

UNCLASSIFIED 

22. PRICE 






































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